Abstracts

We propose a novel approach to identify the origin of pyrite grains and distinguish biologically influenced sedimentary pyrite using combined in situ sulfur isotope (δ34S) and trace element (TE) analyses. To classify and predict the origin of individual pyrite grains, we applied multiple machine-learning algorithms to coupled δ34S and TE data from pyrite grains formed from diverse sedimentary, hydrothermal, and metasomatic processes across geologic time. Our unsupervised classification algorithm, K-means++ cluster analysis, yielded six classes based on the formation environment of the pyrite: sedimentary, low temperature hydrothermal, medium temperature, polymetallic hydrothermal, high temperature, and large euhedral. We tested three supervised models (random forest [RF], Naïve Bayes, k-nearest neighbors), and RF outperformed the others in predicting pyrite formation type, achieving a precision (area under the ROC curve) of 0.979 ± 0.005 and an overall average class accuracy of 0.878 ± 0.005. Moreover, we found that coupling TE and δ34S data significantly improved the performance of the RF model compared with using either TE or δ34S data alone. Our data provide a novel framework for exploring sedimentary rocks that have undergone multiple hydrothermal, magmatic, and metamorphic alterations. Most significant, however, is the demonstrated potential for distinguishing between biogenic and abiotic pyrite in samples from early Earth. This approach could also be applied to the search for potential biosignatures in samples returned from Mars.

Inductively coupled plasma-mass spectrometry (ICP-MS) trace element analysis was used to characterize raw chert from one secondary (LeDx-42) and two primary (LbDt-1 and LdDx-2) sources on southern Baffin Island, Nunavut, Canada. Raw chert trace element data are compared to ICP-MS trace element data for chert artifacts from a nearby Palaeo-Eskimo archaeological site (LeDx-42). Geochemical consistencies identified among the analyzed samples support the inference that Palaeo-Eskimo toolmakers at LeDx-42 exploited LdDx-2 and LbDt-1 as chert source locations.

The Leo Pargil dome (LPD) in northwest India exposes an interconnected network of pre-, syn-, and post-kinematic leucogranite dikes and sills that pervasively intrude amphibolite-facies metapelites of the mid-crustal Greater Himalayan sequence. Leucogranite bodies range from thin (5-cm-wide) locally derived sills to thick (2-m-wide) crosscutting dikes extending at least 100 m. Three-dimensional exposures elucidate crosscutting relations between different phases of melt injection and crystallization. Combined laser ablation inductively coupled plasma mass spectrometry U–Th/Pb geochronology and trace element analysis on well-characterized monazite grains from nineteen representative leucogranites yields a large, internally consistent data set of approximately 700 U–Th/Pb and 400 trace element analyses. Grain-scale variations in age correlate with trace element distributions and indicate semi-continuous crystallization of monazite from 30 to 18 Ma. The youngest U–Th/Pb ages in a given sample are consistent with the outcrop-scale crosscutting relations, whereas older ages within individual samples record inheritance from partially crystallized melt and source metapelites. U–Th/Pb isotopic and trace element data are incorporated into a model of melting within the LPD that involves (1) steady-state equilibrium batch melting of compositionally homogeneous metapelitic sources; (2) pulses of increased melt mobility lasting 1–2 m.y. resulting in segregation of melt from its source and amalgamation into mixed magmas; and (3) rapid emplacement and final crystallization of leucogranite bodies. Melt systems in the LPD evolved from locally derived, in situ melt in migmatitic source rocks into a vast network of dikes and sills in the overlying non-migmatitic host rocks.

Rainfall in Hawaii

Diagenetic history of sedimentary carbonates: Constraints from combined cathodoluminescence and trace element analyses by micro-PIXE

Major and trace element compositions (including REE) of mineral, thermal, mine and surface waters in SW Germany and implications for water–rock interaction

Due to the remarkable properties achieved under ambient conditions and with quite limited components, mollusk shells are very appealing natural bio-composites used as inspiration for new advanced materials. Calcium carbonate which is among the most widespread biominerals is used by mollusks as a building material that constitutes 95-99% of their shells. Within the investigation of calcium carbonate polymorphs present in the shells, diverse theoretical and experimental studies were performed, however, further research of these crystalline forms is required. There are very little researches on the energy landscapes of biogenic calcium carbonate which can provide us information about the free energies of already known as well as newly discovered plausible structures. To investigate the structural, mechanical, elastic, or vibrational properties and to predict new possible structures of biogenic calcium carbonate, different calculation methods could be employed. Some of these studies are presented and discussed in this paper.

The Mediterranean Sea is a large sea almost completely enclosed by Europe, Africa, and SW Asia. Today, the continuous flow of Atlantic seawater through the Strait of Gibraltar balances the net water loss due to the excess of evaporation over input from rain and rivers and keeps the Mediterranean a marine basin with the water level equal to the global ocean level. In the late Miocene, the input of Atlantic seawater was through shallow gateways in southern Spain and northern Morocco. The exhumation of the Betic and Rif Cordilleras and orbitally-controlled regional climate change contributed to the step-by-step close these marine gateways and transformed the Mediterranean into an inhospitable evaporitic sea, starting at 5.96±0.02 Ma. The environmental and hydrological crisis that followed, known as the Messinian Salinity Crisis, peaked at ~5.55 Ma, when a 1.5-2 km-thick salt layer precipitated on the sea floor, and terminated at ~5.332 Ma, when normal marine conditions were re-established, perhaps as a consequence of catastrophic flooding at Gibraltar. The transitional interval from the giant salina to Mediterranean Sea that resembles what we know today is known as the Lago-Mare phase. Gypsum and brackish water biota from the Central Paratethys (approximately coinciding with the present-day Hungary-Slovenia) are both characteristic of Lago-Mare successions. This sedimentary and paleontological evidence suggest that the Mediterranean, during the Lago-Mare phase, experienced a complex history of inter- and extrabasinal connections, base-level fluctuations and extreme environmental and biological changes. This thesis aims to reconstruct the fiercely debated Mediterranean water level changes and identify the hydrological fluxes responsible for these Lago-Mare environmental and biological turnover events. It focuses on key sections exposed on-land and recovered from deep sea cores along an E-W transect across the Mediterranean with a multi-disciplinary approach that integrates biocyclostratigraphic analyses with high-resolution Sr-isotope ratios. The new data show that the Lago-Mare phase was a far more dynamic period of the Mediterranean history than previously thought. Large areas of the Mediterranean were occupied by an anomalohaline water mass predominantly formed by low-salinity waters from the Eastern Paratethys (i.e. the present-day Black-Caspian seas) and from the larger circum-Mediterranean rivers such as the Nile, the Rhône and currently dried North-African rivers. A small and possibly episodic Atlantic flux was a minor contributor. The regular variability of the Mediterranean’s freshwater budget with the astronomic precession combined with fluctuating Atlantic inflow and negligible outflow resulted in a Mediterranean base level that oscillated dramatically, but consistently below eustatic sea level. These precession-paced fluctuations caused the low-salinity Paratethyan biota to colonize the marginal areas of the Mediterranean at times of high base level and central areas during phases of low base level, gypsum to precipitate only in the deeper basins during the regressive phases and silled regions such as the Adriatic and the North Aegean to exist for long as some of the largest endorheic lakes.

Mg/Ca profiles within archaeological mollusc (Patella vulgata) shells: Laser-Induced Breakdown Spectroscopy compared to Inductively Coupled Plasma-Optical Emission Spectrometry

Human migration into Europe during the late Early Pleistocene climate transition

We report the results of new stable oxygen and carbon isotope analyses on carbonate fine fraction, whole rock, and benthic foraminifers, CaCO3and coarse fraction percentage determinations, and trace element (Sr) analyses on carbonate constituents across the Cretaceous/Tertiary (K/T) boundary in Deep Sea Drilling Project (DSDP) sites 47.2, 356, 384, and 577 and compare them with published results from K/T boundary sections in other DSDP sites. We used the trace element data and scanning electron microscope examination to evaluate possible diagenetic alteration and relative preservation of the samples analyzed in this study. The ∂18O data when interpreted as isotopic paleotemperatures indicate relative stable surface water and deepwater temperatures in the late Maestrichtian followed by somewhat fluctuating temperatures in the early Paleocene. However, there is no indication of either a significant warming or cooling at or following the K/T boundary. Several sites do exhibit somewhat heavier ∂18O values by about 0.5‰ across the boundary, which might suggest a 2‐3°C cooling at most. However, we interpret these somewhat heavier ∂18O values as reflecting slightly better preservation of ∂18O of carbonate constitutents in relatively clay‐rich intervals (e.g., lower diagentic potential) characteristic of the K/T boundary. The ∂13C values of carbonate fine fraction and planktonic foraminifers indicate a major negative excursion in surface water total dissolved carbon across the boundary. The surface water and deepwater ∂13C values from benthic foraminifers combined with calculated decreases in carbonate accumulation rates at all sites in the earliest Paleocene are consistent with a major decrease in productivity across the K/T boundary. The decrease in CaCO3accumulation rates is due not to increased rates of dissolution but to decreased production in surface waters. The low‐productivity episode lasted at least 1 m.y. beyond the K/T boundary crisis, suggesting that hypothesized catastrophic events alone, such as impact of an apollo object, are not the only explanation for the observed long‐term decrease in productivity. There is also an indication in the ∂13C curves from several sites that the surface water ∂13C decrease began in the latest Maestrichtian, suggesting that the decrease in productivity may have been independent of a hypothesized impact event.

Carbonates and cherts in the 3.35 billion-year-old Strelley Pool Formation (Fm.; Australia) host stromatolites that are among the oldest remnants of life on Earth. However, it is still not entirely clear whether these mineral phases are authigenic precipitates, and whether they represent reliable geochemical archives of early Earth environments. Here we present major/trace-element and Nd-isotope data of stromatolitic carbonates, associated crystal-fan carbonates, and cherts in the Strelley Pool Fm. (i) to assess the reliability of these chemical sediments as geochemical archives of the fluids from which they precipitated, (ii) to date the time of formation of carbonate and silica phases, and (iii) to trace the sources of elements prevailing in microbial habitats 3.35 Ga ago.Stromatolitic carbonates plot together with the stratigraphically underlying Marble Bar cherts on a Sm-Nd regression line yielding 3253 ± 320 Ma. In contrast, associated crystal-fan carbonates together with altered Marble Bar cherts yield 2718 ± 220 Ma, suggesting that their Sm-Nd isotope system was reset after deposition. Both types of carbonates, as well as white cherts, show shale-normalized rare earth element and yttrium patterns (REYSN; with the exception of redox-sensitive Ce and Eu and heavy REYSN to middle REYSN depletion) that are parallel to those of modern seawater, indicating a predominantly seawater-derived origin. Positive EuSN anomalies (2.1–2.4), combined with heterogeneous ɛNd3.35Ga values between −3.2 and +5.8 within individual alternating stromatolite laminae, further support that the dissolved fraction of seawater on the ancient carbonate platform was variably affected by both continental weathering and high-temperature hydrothermal fluids contributing elements of both young mafic or older felsic rocks. In conclusion, trace element and Nd isotope data presented here match well with the depositional environment, as characterized based on lithological, geochemical, and stratigraphic relationships, on an early continent, showing at least episodic emergence above the sea level, supporting microbial life on a shallow marine platform.

Andalusia's lowland countryside has a network of small geographically isolated playa lakes scattered across an area of 9000 km2 whose watersheds are mostly occupied by clayey rocks. The hydrological model proposed by the authors seeks to find equilibrium among usefulness, simplicity, and applicability to isolated playas in a semiarid context elsewhere. Based in such model, the authors have used monthly climatic data, water stage measurements, and the basin morphometry of a particular case (Los Jarales playa lake) to calibrate the soil water budget in the catchment and the water inputs from the watershed (runoff plus groundwater flow) at different scales, from monthly to daily. After the hydrologic model was calibrated, the authors implemented simulations with the goal of reproducing the past hydrological dynamics and forecasting water regime changes that would be caused by a modification of the wetland morphometry.

The hydrological functioning of wetlands in S Spain is poorly understood. We perform a 22-years hydrological modelling of seven playa-lakes located in a semi-arid region of southern Spain, including dry and wet periods. To do that, we applied a hydrological balance model to reconstruct past lake water levels. In addition, we investigated the hydrochemistry of the water, the basin bathymetry, and the geological setting of the watersheds, acquiring new lithology and active structures data. Once the models were constrained, scenarios considering increases on temperature and human management were implemented, and discussed. The water balance is simplified to precipitation (water input) and basin discharge (evapotranspiration), as the lakes are disconnected from groundwater because of the low-permeability substrate. In addition, unlike in previous studies, we add overflows to the modelling. The results of the model agree with actual lake water monitoring data (R2 > 0.8). We observed that the hydroperiods of some of these lakes vary from permanent lakes to ephemeral, depending strongly on the basin bathymetry. Lakes with steeply margins show longer hydroperiods, whilst it is shorter for low-lying floor playa-lakes. In addition, we observed that steeply lake margins respond to active faults and/or lithological changes. To forecast the effects of climate change on the lake hydroperiods, we applied a 1 °C increase in average temperature in our hydrological modelling. The hydroperiod is significantly reduced for ephemeral playa-lakes, whilst is barely affected in permanent lakes. Moreover, we detected the high sensitivity of ephemeral playa-lakes to the anthropogenic management, including siltation, plant colonization and changes watershed surface.

Loess deposits are widely distributed across the globe and provide detailed records of climatic changes since the Quaternary period. Their geochemical element characteristics are important indicators of paleoenvironmental evolution and provenance. Therefore, four typical loess sections from four different islands of the Miaodao Islands were selected for systematically geochemical analysis of major and trace elements. The geochemical data of major and trace elements are very similar, indicating that the loess of all islands on the Miaodao have a common provenance. The geochemical test results show that t SiO2, Al2O3, Fe2O3 and CaO are the major chemical components of loess, with an average total content of 85–90%. The average Eu/Eu*, ΣLREE/ΣHREE, LaN/YbN, GdN/YbN values of the Miaodao Islands loess range from 0.65 to 0.69, 7.84 to 8.31, 8.02 to 9.99, 1.40 to 1.76. These data are similar to and different from those of the Chinese Loess Plateau, indicating the diversity of Miaodao Islands Loess provenance. The CIA (Chemical Index of Alteration) (50–65) and Na/K results suggest that the loess here had experienced incipient chemical weathering. The A-CN-K (Al2O3-CaO* + Na2O-K2O) diagram indicates that the weathering trend of the loess sections is consistent with that of continental weathering. The local loess data points are close and parallel to the A-CN line, suggesting that the loess dust material on the Miaodao Islands originated from the extensive upper continental crust, and was highly mixed in the process of wind transport and deposition. The relationships of Log[(CaO + Na2O)/K2O] versus Log(SiO2/Al2O3), Na2O/Al2O3 versus K2O/Al2O3, LaN/YbN versus Eu/Eu*, Sc-Th-La and Zr-Sc-Th plots of major and trace elements reveal that the loess sources for the Miaodao Islands are similar to those of the Loess Plateau, which were derived from alluvial fan deposits flanking the Qilian Shan in China, the Gobi Altay and Hangayn Mountains in Mongolia. However, the loess of the Miaodao Islands is coarser in average grain size and contains abundant marine fossils, with gravel layers, indicating it is allochthous and near-source, which suggests it mainly originated from the adjacent exposed sea floor sediments of the Bohai Sea during glacial periods. Finally, we conclude that the loess of the Miaodao Islands is the result of a gradual accumulation process, in which the relative amount of distant-source material decreased and the near-source material increased in response to changes in sea level and paleoclimate. Our findings support that the loess of the Miaodao Islands was formed by mixing material from distant and proximal sources.