Sulfur and oxygen isotope compositions of Upper Triassic sulfates from northern Apennines (Italy) : paleogeographic and hydrogeochemical implications

Upper Triassic bedded evaporite sulfate of the Burano Formation outcropping at Cerreto Pass between Tuscany and Emilia-Romagna in the Northern Apennines were analyzed for sulfur and oxygen isotope compositions, yielding d34S and d18O values of 15.5±0.4‰ and 10.8±1.2‰, respectively (mean ±99% confidence intervals). Combining these values with those of other Burano Formation sulfate deposits along the Apennine chain, mean for d34S and d18O values are obtained (15.2±0.2‰ and 10.9±0.5‰, respectively). These isotopic signatures are interpreted as preserved primary features, despite the fact that the Burano Formation underwent anchizone to epizone metamorphism during the Apennine orogenesis. An overall d18O value of 10.9±1.5‰ (mean ± pooled standard deviation), obtained by combining consistent sets of data from Italy and Spain, closely approaches that of gypsum deposited from the Tethys ocean during the Late Triassic. In addition, reviewing the isotope data published on Late Triassic evaporite sulfates from the Mediterranean area and abroad, several d34S values appear to be lower than the inferred primary isotopic signature, and seemly decrease from East to West in the Mediterranean region, suggesting a similar trend for the Tethys ocean sulfate. Possibly, 34S-depleted sulfate entered the ocean through oxidation of volcanic SO2 emitted in the atmosphere and degassed from the seafloor during the development of Late Triassic rifting. On the other hand, positive shifts of d34S and d18O values also occur, defining a common trend that may be related to synsedimentary biological effects or post-depositional metasomatic-metamorphic effects, the latter affecting particularly the d18O signature. Therefore, the d34S and d18O signatures of evaporite sulfate may provide a like "slide-rule" diagram to distinguish between isotopic effects related to biological or abiological processes, thus contributing to the reconstruction of paleoenvironments and paleogeographic settings. Based on the d34S-d18O "slide-rule", the isotopic composition of sulfate dissolved in spring and stream waters of northern Tuscany was interpreted in terms of origin of the sulfate and modifying processes in solution. It was concluded that sulfate in springs derives from Upper Triassic evaporite existing locally at depth (Burano Formation), whereas sulfate in streams is manifestly a mixture of Burano Formation sulfate with supergene sulfate from oxidation of sulfide in the rocks. In sulfurous springs, both sulfur and oxygen isotope fractionations with respect to the source sulfate signatures may be ascribed to bacterial effects. However, the oxygen isotope exchange of sulfate with water should have been a very minor process as supported by the nearsurface temperature values estimated by sulfate-water oxygen isotope thermometry

Inferring the diet of extinct elephants: The case study of straight-tusked elephants from Neumark Nord 1 (Northeastern Germany)

Inferring the diet of fossil mammals is a major approach to mammalian palaeobiology and palaeoecology. Compared to other mammals, proboscideans pose significant problems because elephants eat different kinds of food and may change it frequently. Results obtained by analysing the last molars of Palaeoloxodon antiquus from Neumark Nord, highlight the effectiveness of a multidisciplinary approach in inferring the dietary adaptation of elephants. The microwear pattern and stable isotope data obtained for the straight-tusked elephants from Neumark Nord 1, suggest they were mainly grazers in a wooded grassland and moderately humid environment

Sulfur and oxygen isotope compositions of Upper Triassic sulfates from Northerm Apennines (Italy): palaeogeographic and hidrogeochemical implications

Upper Triassic bedded evaporite sulfate of the Burano Formation outcropping at Cerreto Pass between Tuscany and Emilia-Romagna in the Northern Apennines were analyzed for sulfur and oxygen isotope compositions, yielding d34S and d18O values of 15.5±0.4‰ and 10.8±1.2‰, respectively (mean ±99% confidence intervals). Combining these values with those of other Burano Formation sulfate deposits along the Apennine chain, mean for d34S and d18O values are obtained (15.2±0.2‰ and 10.9±0.5‰, respectively). These isotopic signatures are interpreted as preserved primary features, despite the fact that the Burano Formation underwent anchizone to epizone metamorphism during the Apennine orogenesis. An overall d18O value of 10.9±1.5‰ (mean ± pooled standard deviation), obtained by combining consistent sets of data from Italy and Spain, closely approaches that of gypsum deposited from the Tethys ocean during the Late Triassic. In addition, reviewing the isotope data published on Late Triassic evaporite sulfates from the Mediterranean area and abroad, several d34S values appear to be lower than the inferred primary isotopic signature, and seemly decrease from East to West in the Mediterranean region, suggesting a similar trend for the Tethys ocean sulfate. Possibly, 34S-depleted sulfate entered the ocean through oxidation of volcanic SO2 emitted in the atmosphere and degassed from the seafloor during the development of Late Triassic rifting. On the other hand, positive shifts of d34S and d18O values also occur, defining a common trend that may be related to synsedimentary biological effects or post-depositional metasomatic-metamorphic effects, the latter affecting particularly the d18O signature. Therefore, the d34S and d18O signatures of evaporite sulfate may provide a like “slide-rule” diagram to distinguish between isotopic effects related to biological or abiological processes, thus contributing to the reconstruction of paleoenvironments and paleogeographic settings. Based on the d34S-d18O “slide-rule”, the isotopic composition of sulfate dissolved in spring and stream waters of northern Tuscany was interpreted in terms of origin of the sulfate and modifying processes in solution. It was concluded that sulfate in springs derives from Upper Triassic evaporite existing locally at depth (Burano Formation), whereas sulfate in streams is manifestly a mixture of Burano Formation sulfate with supergene sulfate from oxidation of sulfide in the rocks. In sulfurous springs, both sulfur and oxygen isotope fractionations with respect to the source sulfate signatures may be ascribed to bacterial effects. However, the oxygen isotope exchange of sulfate with water should have been a very minor process as supported by the nearsurface temperature values estimated by sulfate-water oxygen isotope thermometry

Isotope partitioning between cow milk and farm water: A tool for verification of milk provenance

Rationale: The oxygen and hydrogen isotope compositions of the water component of the milk from nine Italian dairy farms were studied together with the farm water for one year. The aim was to verify the importance of farm water and seasonal temperature variation on milk isotope values and propose mathematical relations as new tools to identify the milk origin. Methods: Milk was centrifuged to separate the solids and then distilled under vacuum to separate water. δ(18O/16O) and δ(2H/1H) analyses of the water molecules were carried out using a water equilibrator online with a mass spectrometer. For oxygen and hydrogen isotope determination, water was equilibrated with pure CO2 for 7.5 h and with pure H2 for 5 h, respectively. The isotope ratio value is indicated with δ (expressed on the VSMOW/SLAP scale) as defined by IUPAC. Results: The average annual isotope value of milk at the different cattle sheds is mostly related to the farm water suggesting that the drinking water is the most important factor influencing the isotopic values of the milk water. The milk/water fractionation factor correlates with the milking time and, thus, the seasonal temperature is best described by a 4th order polynomial regression line. A two-level check model was used to verify the milking provenance. Conclusions: This study shows that it is essential to analyze both milk and farm water to indicate provenance. A two-step verification tool, based on the difference between the measured and calculated δ(18O/16O)M values, and the difference between the calculated and estimated milk-water fractionation factors, allowed the source determination of milk. Both conditions must be met if the milk is considered to be from the Parmigiano-Reggiano production region. Although this approach was developed for this region, it can easily be tested and adapted to other dairy production areas

Study to optimize the effectiveness of Copper treatments for a low impact viticulture

Among all pathologies that afflict grapevine, Downy Mildew (DM) is the most important. Generally controlled by using Copper (Cu), recently European Commission confirmed its usage but limiting the maximum amount to 28 Kg per hectare in 7 years (Reg. EU 2018/1981). Anyway, in the grape growing context it is difficult to reduce the use of Cu and generally chemicals, due to climate conditions, as well as climate changing. For this instance, Cu treatments have to be improved. Hence, the aims of this work were to determine the possibility to reduce Cu using and evaluating the variation of Cu cladding on grapevine leaves and grapes, in relation to the phytoiatric status. The efficacy level of the Cu protection given to DM and the correlation among them was also assessed. Five organic vineyards located in north-eastern of Italy were selected as experimental sites. Leaves and grapes were sampled during vegetative season and analysed for determining the quantity of elemental Cu by the use of ICP AES. Spreading of DM in vineyards was evaluated as well and the correlation between DM and Cu quantity on leaves and grapes was determined. First results indicate that the mean level of Cu applied by farmers (range: 3.77 to 8.88 µg/cm 2 of Cu on leaves) during vegetative season is not enough to have an optimal protection against DM (diffusion on grapes and leaves: 40 to 50%), although at the maximum amount of Cu, the plant protection effect was quite good. Thus, Cu treatments have to be pondered on the basis of meteorological data and previous infection of DM, so that it will be possible to determine the right quantity of Cu to be applied in correlation to DM presence and weather. As future goals, data will be correlated with image analysis, in order to quickly study the best conditions for Cu application directly on field and having back a real time information of Cu cladding and risk classes of DM infection. In this way, it is possible to reduce inputs in plant defence and then guarantee a quality and sustainable production of grapes, wines and must

Hydrogeological behaviour and geochemical features of waters in evaporite-bearing low-permeability successions: A case study in Southern Sicily, Italy

Knowledge about the hydrogeological behaviour of heterogeneous low-permeability media is an important tool when designing anthropogenic works (e.g., landfills) that could potentially have negative impacts on the environment and on people’s health. The knowledge about the biogeochemical processes in these media could prevent “false positives” when studying groundwater quality and possible contamination caused by anthropogenic activities. In this research, we firstly refined knowledge about the groundwater flow field at a representative site where the groundwater flows within an evaporite-bearing low-permeability succession. Hydraulic measurements and tritium analyses demonstrated the coexistence of relatively brief to very prolonged groundwater pathways. The groundwater is recharged by local precipitation, as demonstrated by stable isotopes investigations. However, relatively deep groundwater is clearly linked to very high tritium content rainwater precipitated during the 1950s and 1960s. The deuterium content of some groundwater samples showed unusual values, explained by the interactions between the groundwater and certain gases (H2S and CH4), the presences of which are linked to sulfate-reducing bacteria and methanogenic archaea detected within the saturated medium through biomolecular investigations in the shallow organic reach clayey deposits. In a wider, methodological context, the present study demonstrates that interdisciplinary approaches provide better knowledge about the behaviour of heterogeneous low-permeability media and the meaning of each data type

Long-term species, sexual and individual variations in foraging strategies of fur seals revealed by stable isotopes in whiskers

Background: Individual variations in the use of the species niche are an important component of diversity in trophic interactions. A challenge in testing consistency of individual foraging strategy is the repeated collection of information on the same individuals. Methodology/Principal Findings: The foraging strategies of sympatric fur seals (Arctocephalus gazella and A. tropicalis) were examined using the stable isotope signature of serially sampled whiskers. Most whiskers exhibited synchronous delta C-13 and delta N-15 oscillations that correspond to the seal annual movements over the long term (up to 8 years). delta C-13 and delta N-15 values were spread over large ranges, with differences between species, sexes and individuals. The main segregating mechanism operates at the spatial scale. Most seals favored foraging in subantarctic waters (where the Crozet Islands are located) where they fed on myctophids. However, A. gazella dispersed in the Antarctic Zone and A. tropicalis more in the subtropics. Gender differences in annual time budget shape the seal movements. Males that do not perform any parental care exhibited large isotopic oscillations reflecting broad annual migrations, while isotopic values of females confined to a limited foraging range during lactation exhibited smaller changes. Limited inter-individual isotopic variations occurred in female seals and in male A. tropicalis. In contrast, male A. gazella showed large inter-individual variations, with some males migrating repeatedly to high-Antarctic waters where they fed on krill, thus meaning that individual specialization occurred over years. Conclusions/Significance: Whisker isotopic signature yields unique long-term information on individual behaviour that integrates the spatial, trophic and temporal dimensions of the ecological niche. The method allows depicting the entire realized niche of the species, including some of its less well-known components such as age-, sex-, individual- and migration-related changes. It highlights intrapopulation heterogeneity in foraging strategies that could have important implications for likely demographic responses to environmental variability

Integrating isotopes and documentary evidence : dietary patterns in a late medieval and early modern mining community, Sweden

We would like to thank the Archaeological Research Laboratory, Stockholm University, Sweden and the Tandem Laboratory (Ångström Laboratory), Uppsala University, Sweden, for undertaking the analyses of stable nitrogen and carbon isotopes in both human and animal collagen samples. Also, thanks to Elin Ahlin Sundman for providing the δ13C and δ15N values for animal references from Västerås. This research (Bäckström’s PhD employment at Lund University, Sweden) was supported by the Berit Wallenberg Foundation (BWS 2010.0176) and Jakob and Johan Söderberg’s foundation. The ‘Sala project’ (excavations and analyses) has been funded by Riksens Clenodium, Jernkontoret, Birgit and Gad Rausing’s Foundation, SAU’s Research Foundation, the Royal Physiographic Society of Lund, Berit Wallenbergs Foundation, Åke Wibergs Foundation, Lars Hiertas Memory, Helge Ax:son Johnson’s Foundation and The Royal Swedish Academy of Sciences.Peer reviewedPublisher PD

A synergistic solution for fighting fraudulent practices in squid using light stable isotope ratios and lanthanide tracers

To identify a novel optimized strategy for preventing fraudulent substitutions of squid species and origins, forty European squids (Loligo vulgaris) and forty flying squids (Todarodes sagittatus) from the Mediterranean Sea and Atlantic Ocean were analyzed for δ13C, δ15N, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, and Lu using isotope ratio mass spectrometry and inductively coupled plasma-mass spectrometry. While δ13C and δ15N variations were mainly species-related, they alone could not reliably distinguish samples. To address this issue, decision rules were developed using Classification and Regression Tree analysis. Threshold values for δ13C (-19.91‰), δ15N (14.87‰), and Pr (0.49 μg kg-1) enabled successful discrimination among Mediterranean European squids, Atlantic European squids, Mediterranean flying squids, and Atlantic flying squids, achieving over 90% accuracy, 81% precision, 80% sensitivity, and 93% specificity. This method holds promise for enhancing traceability and safety in the seafood industry, ensuring product integrity and consumer trust

Tracing deep fluid source contribution to groundwater in an active seismic area (central Italy): A combined geothermometric and isotopic (δ13C) perspective

An understanding of the origin and migration pathways of geofluids in an active seismic area is of paramount importance in terms of societal challenges such as mitigation of seismic hazards. This study investigates the relationship between the stable isotope ratio 13C/12C of deep CO2 and geothermometry in selected groundwater samples located close to extensional faults in central Italy. The temperature range is inferred from an equation based on the Na/Li ratio and chemical geothermal modelling: 113–130 °C. Globally, the calculated temperature range agrees with that resulting from deep boreholes in the Northern Apennines. An alternative method is also included to better evaluate the difference in isotopic composition between the aqueous and gaseous δ13C(CO2) at deep condition. A review of previously published data shows that monitoring of the isotopic composition of the dissolved inorganic carbon (DIC) in springs fed by meteoric origin located in seismically active areas must take into account mass and isotopic balance to correctly evaluate the component, and the role, of deep fluid during seismic events. In particular, the coupled (and corrected) isotope and geothermometrical monitoring of the springs could help to distinguish between deep gas or deep fluid contributions to shallow aquifers. The results of this study indicate that faults play a crucial role in controlling the migration of crustal fluids. In addition, they reveal that possible evaluation of potential seismic precursors mandatorily requires a long period of monthly monitoring