In situ measurements of oxygen isotopic composition in deep-sea coral, Lophelia pertusa: Re-examination of the current geochemical models of biomineralization

We present ion microprobe measurements of oxygen isotopic compositions in the deep-sea coral Lophelia pertusa. Compared to bulk skeletal aragonite fibres, the EMZ (early mineralization zone), near the inside of the calyx, was systematically depleted in ¹⁸O. Rayleigh fractionation from a semi-closed fluid reservoir does not explain this and other geochemical differences. Furthermore, pH values estimated from skeletal δ¹¹B data are inconsistent with the idea that EMZ (or centres of calcification) ¹⁸O depletion reflects a more alkaline calcification environment. Our data, combined with microstructural and geochemical observations, indicate that the aragonitic fibres and EMZ are formed by a compartmentalized mineralization calicoblastic ectoderm, which exerts strong biological control on the composition of the skeleton. Hence, we propose a new model whereby amorphous calcium carbonates (ACC) are precursors to the EMZ, whereas the fibre precipitation is probably governed by kinetic processes.     

Diagenetic effects on the distribution of uranium in live and Holocene corals from the Gulf of Aqaba

We investigated the effects of diagenetic alteration (dissolution, secondary aragonite precipitation and pore filling) on the distribution of U in live and Holocene coral skeletons. For this, we drilled into large Porites lutea coral-heads growing in the Nature Reserve Reef (NRR), northern Gulf of Aqaba, a site close to the Marine Biology Laboratory, Elat, Israel, and sampled the core material and porewater from the drill-hole. In addition, we sampled Holocene corals and beachrock aragonite cements from a pit opened in a reef buried under the laboratory grounds. We measured the concentration and isotopic composition of U in the coral skeletal aragonite, aragonite cements, coral porewater and open NRR and Gulf of Aqaba waters.Uranium concentration in secondary aragonite filling the skeletal pores is significantly higher than in primary biogenic aragonite (17.3 ± 0.6 compared to 11.9 ± 0.3 nmol · g⁻¹, respectively). This concentration difference reflects the closed system incorporation of uranyl tri-carbonate into biogenic aragonite with a U/Ca bulk distribution coefficient (K_D) of unity, versus the open system incorporation into secondary aragonite with K_D of 2.4. The implication of this result is that continuous precipitation of secondary aragonite over ∼1000 yr of reef submergence would reduce the coral porosity by 5% and can produce an apparent lowering of the calculated U/Ca - SST by ∼1°C and apparent age rejuvenation effect of 7%, with no measurable effect on the calculated initial U isotopic composition.All modern and some Holocene corals (with and without aragonite cement) from Elat yielded uniform δ²³⁴U = 144 ± 5, similar to the Gulf of Aqaba and modern ocean values. Elevated δ²³⁴U values of ∼180 were measured only in mid-Holocene corals (∼5000 yr) from the buried reef. The values can reflect the interaction of the coral skeleton with ²³⁴U-enriched ground-seawater that washes the adjacent granitic basement rocks.We conclude that pore filling by secondary aragonite during reef submergence can produce small but measurable effects on the U/Ca thermometry and the U-Th ages. This emphasizes the critical importance of using pristine corals where the original mineralogy and porosity are preserved in paleooceanographic tracing and dating.     

Determination of Radiogenic 87Sr/86Sr and Stable δ88/86SrSRM987 Isotope Values of Thirteen Mineral,Vegetal and Animal Reference Materials by DS‐TIMS

This work presents new ⁸⁷Sr/⁸⁶Sr and δ^88/86Sr_SRM987 isotopic values of thirteen mineral, vegetal and animal reference materials. Except for UB‐N, all our results are consistent with previously published data. Our results highlight intermediate precisions among the best presently published and a non‐significant systematic shift with the calculated δ^88/86Sr_SRM987 mean values for the three most analysed reference materials in the literature (i.e., IAPSO, BCR‐2 and JCp‐1). By comparison with the literature and between two distinct digestions, a significant bias of δ^88/86Sr_SRM987 values was highlighted for two reference materials (UB‐N and GS‐N). It has also been shown that digestion protocols (nitric and multi‐acid) have a moderate impact on the δ^88/86Sr_SRM987 isotopic values for the Jls‐1 reference materials suggesting that a nitric acid digestion of carbonate can be used without significant bias from partial digestion of non‐carbonate impurities. Different δ^88/86Sr_SRM987 values were measured after two independent Sr/matrix separations, according to the same protocol, for a fat‐rich organic reference material (BCR‐380R) and have been related to a potential post‐digestion heterogeneity. Finally, the δ^88/86Sr_SRM987 value differences measured between animal‐vegetal and between coral‐seawater reference materials agree with the previously published results, highlighting an Sr isotopic fractionation along the trophic chain and during carbonate precipitation.     

Compound-specific stable carbon isotope analysis as a tool for correlating coal-sourced oils and interbedded shale-sourced oils in coal measures: an example from Turpan basin, north-western China

Molecular geochemical methods have shown that it is often difficult to differentiate between coal- and interbedded shale-sourced oils, even though coals and interbedded shales may exhibit considerable organic influx variation (e.g. land plant vs algal organic matter) due to the changes of depositional setting. However, compound-specific stable carbon isotopic compositions are sensitive to the source input variations. Typically, specific molecules are more depleted in ¹³C with increasing content of aqueous biota. This hypothesis is examined and exemplified by comparing the stable carbon isotopic ratios of n-alkanes from source rock extracts and related oils of the Turpan basin, north-western China. Stable carbon isotopic values of n-alkanes extracted from coals and interbedded shales show that δ¹³C values of n-alkanes with less than 20 carbon atoms vary only slightly. However, there are dramatic changes in the isotopic compositions of higher molecular weight n-alkanes. Furthermore, n-alkanes from coal extracts are enriched in ¹³C relative to that of interbedded shales with excursions up to 2–3‰. This comparison enables the differentiation of coal- and interbedded shale-sourced oils, and provides information useful in assessing the hydrocarbon system of a basin.     

Minor and trace element incorporation into branching coral Acropora nobilis skeleton

Chemical and isotopic compositions of the Acropora nobilis skeleton were analyzed at various spatial resolutions to investigate the mechanism by which elements are incorporated into the skeleton. Chemical and isotopic profiles along growth axes of axial and radial corallites did not show seasonal variation, with the exception of the δ¹⁸O profile of the axial corallite. Detailed observations of the skeletal structure revealed that the skeletal density increased with distance from the tip because secondarily precipitated aragonite (here called the “infilling” skeleton) filled pore spaces in the “framework” skeleton. Microscale element analyses revealed that main part of the infilling skeleton had lower Mg/Ca and higher Sr/Ca and U/Ca than the framework skeleton. At microscale, Sr/Ca and U/Ca were positively correlated with each other, and negatively correlated with Mg/Ca but only weakly. The results showed that the infilling skeleton differed significantly from the adjacent framework skeleton in terms of not only formation chronology but also chemical composition, and that the bulk composition was influenced by the infilling/framework skeletal ratio. In order to use the Acropora skeleton as a paleoclimate archive, the relationship between environmental factors and the chemical composition of each skeletal component needs to be established.     

The build up of the isotopic signal in skeletons of the stony coral Porites lutea

The build up of the isotopic signal in corals was followed by sampling the newly formed skeleton at a monthly resolution for a period of two years in order to establish the interrelations between the calcification processes and the skeletal isotopic composition. We deployed two underwater sampling schemes, which provide a monitor of the changes in water temperature and δ¹⁸O and in the corresponding newly accreted skeleton of undisturbed Porites lutea colonies under natural conditions and four transplanted colonies, which maintained the genetic identity throughout the experiment. The results indicate that δ¹⁸O of the newly accreted skeleton does not correlate with ambient temperature although the seasonal temperature variability at the site (winter to summer) is in the order of 6 °C and δ¹⁸O of seawater is constant throughout the year. In contrast to the newly formed surface skeleton, the isotopic compositions of the deep and older parts of the skeleton show the predicted annual isotopic pattern with highly significant correlation between δ¹⁸O_s and SST. The transformation between temperature-independent to temperature-dependent isotopic signal occurs several months after the skeleton was formed at the surface. The position of the skeleton in relation to the open sea may generate the difference between δ¹⁸O_s of the surface skeleton and that of the skeleton previously accreted further down the tissue layer. Our data support the general model of a multi-step skeletogenesis process, where the temperature independent skeleton is entails the first step, the production of skeletal scaffold, and the environmental temperature signature is captured by the next two other steps: the thickening and the periodic abrupt uplift occurring at the depth of the tissue layer. However, re-examination and development of the current isotopic models for coral calcification are required in order to explain the observed different temperature dependency during the growth’s sequence.     

Evaluation of oxygen isotopes in carbonate as an indicator of lake evolution in arid areas: The modern Qinghai Lake, Qinghai–Tibet Plateau

The oxygen isotopic composition of carbonate in lakes has been used as a useful indicator in Palaeolimnological research, and has made some important contributions to our understanding of lacustrine systems. For modern lakes in arid or cold areas, however, there are few data available to test the effect of lake salinity and temperature on the oxygen isotopic composition of various carbonate sources such as ostracod, bulk carbonate, and fine-grained carbonate (< 60 μm). Here we examined the oxygen isotopic composition of ostracods, bulk carbonate, and fine-grained carbonates, as well as that of coexisting water from Lake Qinghai and the smaller surrounding lakes and ponds on the Qinghai–Tibet Plateau. Our investigation highlights three key effects. First, the oxygen isotopic composition of ostracods, bulk carbonate, and fine-grained carbonate in the lakes and ponds shows a clear response to lake water δ¹⁸O values, and these vary with water salinity. The relationship between lake water δ¹⁸O and salinity is not only dominated by the evaporation/freshwater input ratios, but is also controlled by the distance to the mouth of the major rivers supplying to the lake. Second, the ostracod, bulk carbonate, and fine-grained carbonate show similar isotopic change trends in the study area, and oxygen isotopic differences between ostracods and authigenic carbonate may be explained by the different water temperatures and very small ‘vital offsets’ of ostracods. Finally, the effect of water depth on temperature leads to increasing δ¹⁸O values in carbonates as water depth increases, both in benthic ostracods living on the lake bottom, as well as in bulk carbonate precipitated at the water surface.For arid, high-altitude Lake Qinghai, our results suggest that variations in the δ¹⁸O values of carbonate in Lake Qinghai are mainly controlled by the oxygen-isotope ratio of the lake water changing with water salinity. As a secondary effect, increasing water depth leads to cooler bottom and surface water, which may result in more positive δ¹⁸O values of ostracod and bulk carbonate.     

Vertical versus horizontal growth strategies of coral frameworks (Tulamben, Bali, Indonesia)

Two different coral framework structures located in a shallow subtidal area on the east coast of Bali are described in this study. One structure is a typical coral carpet with a distinct internal succession of coral taxa and growth forms. It starts with a variety of coral species exhibiting massive, tabular, branching, and platy growth forms settling on volcanic boulders and cobbles. The main body of the coral carpet is composed almost monospecifically of Acropora cf. vaughani, which has filled all accommodating spaces up to the low-water sea level. Mostof this carpet died during the bleaching event of 1998 and the resultant dead Acropora framework is now capped by a platy Montipora assemblage. Some of the Acropora branches within the dead carpet, however, are still alive and display active growth. The Montipora cover protects the dead Acropora framework against mechanical and biological destruction. The few still growing Acropora branches may also contribute to the strength of the framework. The second coral framework is made up almost monogenerically of Montipora. One species of Montipora is of a laminar growth form and produces whorl-like colonies. Within this framework, only part of the Montipora colonies are dead; however, these are intensively fragmented. The fragments have been rapidly settled by a platy Montipora species, which has stabilized the fragments. In this case, the fragment shedding of the Montipora offers the opportunity for progradation of the framework on these fragments. Concerning the Acropora carpet, similar examples from the fossil record of the Miocene era of Spain and Austria have been reported.     

Assessing scleractinian corals as recorders for paleo-pH: Empirical calibration and vital effects

Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ¹¹B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ¹¹B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ¹¹B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.     

Physiological and isotopic responses of scleractinian corals to ocean acidification

Uptake of anthropogenic CO₂ by the oceans is altering seawater chemistry with potentially serious consequences for coral reef ecosystems due to the reduction of seawater pH and aragonite saturation state (Ω_arag). The objectives of this long-term study were to investigate the viability of two ecologically important reef-building coral species, massive Porites sp. and Stylophora pistillata, exposed to high pCO₂ (or low pH) conditions and to observe possible changes in physiologically related parameters as well as skeletal isotopic composition. Fragments of Porites sp. and S. pistillata were kept for 6-14 months under controlled aquarium conditions characterized by normal and elevated pCO₂ conditions, corresponding to pH_T values of 8.09, 7.49, and 7.19, respectively. In contrast with shorter, and therefore more transient experiments, the long experimental timescale achieved in this study ensures complete equilibration and steady state with the experimental environment and guarantees that the data provide insights into viable and stably growing corals. During the experiments, all coral fragments survived and added new skeleton, even at seawater Ω_arag < 1, implying that the coral skeleton is formed by mechanisms under strong biological control. Measurements of boron (B), carbon (C), and oxygen (O) isotopic composition of skeleton, C isotopic composition of coral tissue and symbiont zooxanthellae, along with physiological data (such as skeletal growth, tissue biomass, zooxanthellae cell density, and chlorophyll concentration) allow for a direct comparison with corals living under normal conditions and sampled simultaneously. Skeletal growth and zooxanthellae density were found to decrease, whereas coral tissue biomass (measured as protein concentration) and zooxanthellae chlorophyll concentrations increased under high pCO₂ (low pH) conditions. Both species showed similar trends of δ¹¹B depletion and δ¹⁸O enrichment under reduced pH, whereas the δ¹³C results imply species-specific metabolic response to high pCO₂ conditions. The skeletal δ¹¹B values plot above seawater δ¹¹B vs. pH borate fractionation curves calculated using either the theoretically derived α_B value of 1.0194 (Kakihana et al. (1977) Bull. Chem. Soc. Jpn.50, 158) or the empirical α_B value of 1.0272 (Klochko et al. (2006) EPSL248, 261). However, the effective α_B must be greater than 1.0200 in order to yield calculated coral skeletal δ¹¹B values for pH conditions where Ω_arag ? 1. The δ¹¹B vs. pH offset from the seawater δ¹¹B vs. pH fractionation curves suggests a change in the ratio of skeletal material laid down during dark and light calcification and/or an internal pH regulation, presumably controlled by ion-transport enzymes. Finally, seawater pH significantly influences skeletal δ¹³C and δ¹⁸O. This must be taken into consideration when reconstructing paleo-environmental conditions from coral skeletons.     

Carbonate precipitation in the alkaline lake Specchio di Venere (Pantelleria Island,Italy) and the possible role of microbial mats

Alkaline lakes like the hydrothermally affected lake Specchio di Venere (Pantelleria Island, Central Mediterranean) are typical geological settings harbouring calcified microbial mats. The present work is focused on the discrimination between biotic and abiotic processes driving carbonate precipitation in this lake, using hydrochemical, mineralogical and isotopic data. Hydrochemical analyses demonstrate that the lake is nearly 10−fold supersaturated with regard to aragonite and seasonally reaches hydromagnesite supersaturation. Microscopic observations depict organosedimentary laminated structures consisting of microbial communities and aragonitic precipitates, which are rather disseminated in pores than directly linked to microorganisms. Oxygen isotopic data indicate that authigenic carbonate crystallisation from evaporating water is the dominant precipitation process, further suggested by the absence of textural evidence of diagenetic processes. Conversely, the observed δ¹³C values reflect an influence of extracellular polymeric substances (EPS) on carbon fractionation during the precipitation process, due to the selective sequestration of ¹²C in the biomass. The above considerations suggest that at lake Specchio di Venere the carbonate precipitation is mainly of inorganic nature, but a minor role played by biologically influenced processes in microbial mats is not excluded.     

Rayleigh-based, multi-element coral thermometry: A biomineralization approach to developing climate proxies

This study presents a new approach to coral thermometry that deconvolves the influence of water temperature on skeleton composition from that of “vital effects”, and has the potential to provide estimates of growth temperatures that are accurate to within a few tenths of a degree Celsius from both tropical and cold-water corals. Our results provide support for a physico-chemical model of coral biomineralization, and imply that Mg²⁺ substitutes directly for Ca²⁺ in biogenic aragonite. Recent studies have identified Rayleigh fractionation as an important influence on the elemental composition of coral skeletons. Daily, seasonal and interannual variations in the amount of aragonite precipitated by corals from each “batch” of calcifying fluid can explain why the temperature dependencies of elemental ratios in coral skeleton differ from those of abiogenic aragonites, and are highly variable among individual corals. On the basis of this new insight into the origin of “vital effects” in coral skeleton, we developed a Rayleigh-based, multi-element approach to coral thermometry. Temperature is resolved from the Rayleigh fractionation signal by combining information from multiple element ratios (e.g., Mg/Ca, Sr/Ca, Ba/Ca) to produce a mathematically over-constrained system of Rayleigh equations. Unlike conventional coral thermometers, this approach does not rely on an initial calibration of coral skeletal composition to an instrumental temperature record. Rather, considering coral skeletogenesis as a biologically mediated, physico-chemical process provides a means to extract temperature information from the skeleton composition using the Rayleigh equation and a set of experimentally determined partition coefficients. Because this approach is based on a quantitative understanding of the mechanism that produces the “vital effect” it should be possible to apply it both across scleractinian species and to corals growing in vastly different environments. Where instrumental temperature records are available, a Rayleigh-based framework allows the effects of stress on coral calcification to be identified on the basis of anomalies in the skeletal composition.     

The influence of air mass source on the seasonal isotopic composition of precipitation, eastern USA

As part of the AIRMoN program, daily precipitation samples have been collected since the early 1990s throughout the eastern and central United States. Using precipitation stable isotope (δ¹⁸O and δD) and HYSPLIT back trajectory analysis of 591 samples collected by the AIRMoN program from Florida, Illinois, Pennsylvania, Tennessee, Vermont, and West Virginia, amount weighted seasonal average isotopic compositions were calculated for precipitation from Continental, Pacific, Gulf of Mexico, Arctic, North Atlantic, and Mid Atlantic sources. Our results suggest that these sources are isotopically distinct and variable at and among most sites during most seasons. However, in many instances, the isotopic differences of the sources require dramatic changes in precipitation amounts from these sources to modify the seasonal average isotopic composition at a particular site. The relative importance of each source type to the seasonal average isotopic composition is highly variable among and within sites. The largest differences in the isotopic compositions of different sources are in winter and spring precipitation from the high latitude sites. At the Vermont location, the seasonal average isotopic composition is potentially quite sensitive to the relative amounts of precipitation from Arctic and Gulf of Mexico sources.     

Organic matter in a low productivity anoxic intraplatform basin in the Triassic Tethys

This paper presents isotopic, bulk geochemical and biomarker data measured on organic matter accumulated in a narrow extensional basin developed at the oceanward margin of the huge Triassic carbonate platform in the Alps–Appenines domain. The integration of isotope signatures, organic petrographical and biomarker evidence together with the composition of kerogen pyrolysates suggests immature organic matter predominantly of algal origin with a minor, but not negligible, higher plant derived and moderate bacterial contribution for the entire sequence. The mineral sources are dominated by platform-derived subtidal Dachstein limestone with a minor palaeosol input and a moderate contribution of autochtonous quartz. Nevertheless, parallel variations observed in the mineral content, as well as in the amount and the quality of the organic matter reflect variations in the palaeoenvironment. The increased humidity, existing in the period of the accumulation of the upper section of the sequence, led to the restriction of dolomitization. A slightly greater higher plant derived contribution, in this section, is evidenced by the composition of bitumen and the results on GC and GC/MS analyses on the non-aromatic hydrocarbon fraction of bitumen. Moreover, the climate-induced weathering enchanced the primary productivity and resulted in a pronounced increase in the TOC content. The average estimated value of the planktonic productivity is about three times higher for the calcite-rich sequence than the dolomite-rich one, being 44.2 and 15.3 tC_org/m²/Ma, respectively. The low to moderate planktonic productivity shows that anoxic conditions, observed for the entire succession, are a consequence of the stagnant water stratification rather than high planktonic productivity. Depth trends in the data measured on kerogens (HI, OI, δ¹³Corg values, composition of pyrolysate) together with the δ¹⁸O excursions and Δδ¹³C values appear to be controlled by sea-level fluctuations. Consistent with the high abundance of alkyltiophenes in kerogen pyrolysates, the high S_org/C ratios (ranging between 0.05 and 0.10) suggest the importance of natural sulfurization in the formation of the sulfur-rich type-II-S kerogen occurring in all of the samples.     

Carbon and nitrogen utilization in two species of Red Sea corals along a depth gradient: Insights from stable isotope analysis of total organic material and lipids

We examined the utilization of carbon and nitrogen in two common Red Sea coral species (Stylophora pistillata and Favia favus), differing in colony morphology and polyp size, along a depth gradient down to 60 m. We describe the changes in C/N ratios and in the stable isotope composition of carbon and nitrogen of coral’s tissue and algal symbionts. We also measured the carbon isotopic composition of the lipid fraction extracted from both coral tissue and algal symbionts in order to reveal the changes in the carbon source utilized by the host coral for lipid synthesis.The results show that for both species, δ¹³C decreases by 7–8‰ in animal tissue, algal symbionts and in the lipid fractions as depth increases. However, in contrast to previous reports, the difference between δ¹³C values of coral tissue and algal symbionts does not increase with depth. δ¹⁵N values of coral tissue and algal symbionts in both species do not correlate with depth suggesting that the heterotrophic capacity of these corals does not increase with depth. δ¹³C values of tissue lipids were depleted by an average of 3.5‰ compared to δ¹³C of the entire tissue at all depths. δ¹³C values of algal lipids were depleted by an average of 2‰ compared to δ¹³C of the entire zooxanthellae at all depths, indicating high efficiency of carbon recycling between the two symbiotic partners along the entire gradient. The depletion of lipids is attributed to the fractionation mechanism during lipid synthesis. In addition, for both species, δ¹³C values of algal lipids were enriched compared with δ¹³C of tissue lipids. In S. pistillata, the difference between δ¹³C values of tissue lipids and algal lipids increased linearly with depth, indicating a change in the sources of carbon utilized by the coral for lipid synthesis below 20 m from an autotrophic to a heterotrophic source. However, in F. favus, this average difference was 4 times larger compared to shallow S. pistillata and was constant along the entire depth gradient, suggesting that F. favus uses heterotrophically-acquired carbon for lipid synthesis regardless of depth. Overall, F. favus exhibited enriched δ¹³C and δ¹⁵N values compared to S. pistillata along the entire gradient. We attribute these differences to both morphological differences (i.e. colony morphology, tissue thickness and polyp size) between the two species and to a higher heterotrophy/autotrophy ratio in F. favus at all depths. The C/N ratio in S. pistillata tissue decreased with increasing water depth whereas in F. favus it remained constant. This reflects a higher heterotrophic capacity in the large polyped F. favus, at all depths.     

Isotopic and molecular composition of coal-bed gas in the Amasra region (Zonguldak basin—western Black Sea)

Previous studies on the coal-bed methane potential of the Zonguldak basin have indicated that the gases are thermogenic and sourced by the coal-bearing Carboniferous units. In this earlier work, the origin of coal-bed gas was only defined according to the molecular composition of gases and to organic geochemical properties of the respective source rocks, since data on isotopic composition of gases were not available. Furthermore, in the western Black Sea region there also exist other source rocks, which may have contributed to the coal-bed gas accumulations. The aim of this study is to determine the origin of coal-bed gas and to try a gas-source rock correlation. For this purpose, the molecular and isotopic compositions of 13 headspace gases from coals and adjacent sediments of two wells in the Amasra region have been analyzed. Total organic carbon (TOC) measurements and Rock-Eval pyrolysis were performed in order to characterize the respective source rocks. Coals and sediments are bearing humic type organic matter, which have hydrogen indices (HI) of up to 300 mgHC/gTOC, indicating a certain content of liptinitic material. The stable carbon isotope ratios (δ¹³C) of the kerogen vary from −23.1 to −27.7‰. Air-free calculated gases contain hydrocarbons up to C₅, carbon dioxide (<1%) and a considerable amount of nitrogen (up to 38%). The gaseous hydrocarbons are dominated by methane (>98%). The stable carbon isotope ratios of methane, ethane and propane are defined as δ¹³C₁: −51.1 to −48.3‰, δ¹³C₂: −37.9 to −25.3‰, δ¹³C₃: −26.0 to −19.2 ‰, respectively. The δD₁ values of methane range from −190 to −178‰. According to its isotopic composition, methane is a mixture, partly generated bacterially, partly thermogenic. Molecular and isotopic composition of the gases and organic geochemical properties of possible source rocks indicate that the thermogenic gas generation took place in coals and organic rich shales of the Westphalian-A Kozlu formation. The bacterial input can be related to a primary bacterial methane generation during Carboniferous and/or to a recent secondary bacterial methane generation. However, some peculiarities of respective isotope values of headspace gases can also be related to the desorption process, which took place by sampling.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

Molecular isotopic heterogeneity of fossil organic matter: implications for δCbiomass and δCpalaeoatmosphere proxies

The degree of isotopic variation in fossil organic matter renders bulk δ¹³C signatures strongly influenced by molecular isotopic heterogeneity. For example, in fossil wood the relative abundance of less depleted ¹³C moieties, i.e. preserved ¹³C enriched polysaccharides versus the relatively ¹³C depleted lignin moieties, can be seen to significantly bias δ¹³C_{fossil wood} values. Moreover the variation in δ¹³C values of specific compounds within fossil material are themselves highly variable and reflect the heterogeneity in isotopic values of different carbon atoms within individual compounds. For studies using δ¹³C values of fossil plant material as proxies (e.g., for δ¹³C_{palaeoatmosphere}, δ¹³C_biomass) it is recommended that the biases introduced through molecular heterogeneity, preservation type and taxonomic status of the fossil material are determined initially. Biases inherent in the bulk signature can then be reduced, rendering this value more robust. Alternatively, compound specific stable carbon isotope measurements of individual moieties preserved through geological time might prove to be an alternative proxy for monitoring changes in the bulk δ¹³C value of the plant and might reveal atmospherically induced trends.     

Microenvironmental controls on mineralogy and habit of CaCO3 precipitates: an example from an active travertine system

Analysis of water and associated carbonate precipitates from a small, warm-spring travertine system in SW Colorado, USA, provide an example of the: (i) great variability of the geochemical parameters within these dynamic systems, and (ii) significance of the microenvironment in controlling mineralogy and morphology of carbonate precipitates. Waters emerged from the springs highly charged in CO₂, with an initial p_CO2 of 1.2 × 10⁵ Pa. Degassing of the CO₂ from the waters decreased the pH from 6.1 to 8.0, resulting in an increase of 8%‰ in δ¹³C values downflow in the total CO₂ in solution and an increase in the I_SAT from 2.1 to as high as 63 times supersaturation with respect to calcite. Due to changes in the stable isotopic composition of the waters downflow as well as changes in the degree of supersaturation, stable isotopic analyses range greatly from locale to locale within this small system. Near the spring vents, at relatively low I_SAT levels, well-developed rhombohedra of calcite formed as biotically induced precipitates around diatom stalks and other algae as well as abiotic crusts. In contrast, near the distal end of the system, very high I_SAT levels were reached and resulted in the precipitation of skeletal-dendritic crystals of calcite on copper substrates, floating rafts of laterally linked hemispheres of aragonite crystals, and bimineralic carbonate-encrusted bubbles. Microenvironmental parameters control the mineralogy and habit of these precipitates.     

Oxygen isotopic fractionation during inorganic calcite precipitation ― Effects of temperature, precipitation rate and pH

Stable oxygen isotopic fractionation during inorganic calcite precipitation was experimentally studied by spontaneous precipitation at various pH (8.3 < pH < 10.5), precipitation rates (1.8 < log R < 4.4 μmol m^− 2 h^− 1) and temperatures (5, 25, and 40 °C) using the CO₂ diffusion technique.The results show that the apparent stable oxygen isotopic fractionation factor between calcite and water (α_{calcite–water}) is affected by temperature, the pH of the solution, and the precipitation rate of calcite. Isotopic equilibrium is not maintained during spontaneous precipitation from the solution. Under isotopic non-equilibrium conditions, at a constant temperature and precipitation rate, apparent 1000lnα_{calcite–water} decreases with increasing pH of the solution. If the temperature and pH are held constant, apparent 1000lnα_{calcite–water} values decrease with elevated precipitation rates of calcite. At pH = 8.3, oxygen isotopic fractionation between inorganically precipitated calcite and water as a function of the precipitation rate (R) can be described by the expressions

at 5, 25, and 40 °C, respectively.The impact of precipitation rate on 1000lnα_{calcite–water} value in our experiments clearly indicates a kinetic effect on oxygen isotopic fractionation during calcite precipitation from aqueous solution, even if calcite precipitated slowly from aqueous solution at the given temperature range. Our results support Coplen's work [Coplen T. B. (2007) Calibration of the calcite–water oxygen isotope geothermometer at Devils Hole, Nevada, a natural laboratory. Geochim. Cosmochim. Acta 71, 3948–3957], which indicates that the equilibrium oxygen isotopic fractionation factor might be greater than the commonly accepted value.