Experimental constraints on Li isotope fractionation during clay formation

Knowledge of the lithium (Li) isotope fractionation factor during clay mineral formation is a key parameter for Earth sys-tem models. This study refines our understanding of isotope fractionation during clay formation with essential implicationsfor the interpretation of field data and the global geochemical cycle of Li. We synthesised Mg-rich layer silicates (stevensiteand saponite) at temperatures relevant for Earth surface processes. The resultant solids were characterised by X-ray diffrac-tion (XRD) and Fourier-transform infrared spectroscopy (FT-IR) to confirm the mineralogy and crystallinity of the product.Bulk solid samples were treated with ammonium chloride to remove exchangeable Li in order to distinguish the Li isotopicfractionation between these sites and structural (octahedral) sites. Bulk solids, residual solids and exchangeable solutions wereall enriched in6Li compared to the initial solution. On average, the exchangeable solutions hadd7Li values 7?lower than theinitial solution. The average difference between the residual solid and initial solutiond7Li values (D7Liresidue-solution) for the syn-thesised layer silicates was?16.6 $\pm$ 1.7?at 20?C, in agreement with modelling studies, extrapolations from high tempera-ture experimental data and field observations. Three bonding environments were identified from7Li-NMR spectra which werepresent in both bulk and residual solid7Li-NMR spectra, implying that some exchangeable Li remains after treatment withammonium chloride. The7Li-NMR peaks were assigned to octahedral, outer-sphere (interlayer and adsorbed) and pseudo-hexagonal (ditrigonal cavity) Li. By combining the7Li-NMR data with mass balance constraints we calculated a fractionationfactor, based on a Monte Carlo minimum misfit method, for each bonding environment. The calculated values are?21.5$\pm$ 1.1?,?0.2 $\pm$ 1.9?and 15.0 $\pm$ 12.3?for octahedral, outer-sphere and pseudo-hexagonal sites respectively (errors 1r).The bulk fractionation factor (D7Libulk-solution) is dependent on the chemistry of the initial solution. The higher the Na concen-tration in the initial solution the lower the bulkd7Li value. We suggest this is due to Na outcompeting Li for interlayer sitesand as interlayer Li has a highd7Li value relative to octahedral Li, increased Na serves to lower the bulkd7Li value. Threeexperiments conducted at higher pH exhibited lowerd7Li values in the residual solid. This could either be a kinetic effect,resulting from the higher reaction rate at high pH, or an equilibrium effect resulting from reduced Li incorporation in theresidual solid and/or a change in Li speciation in solution.This study highlights the power of7Li-NMR in experimental studies of clay synthesis to target site specific Li isotope frac-tionation factors which can then be used to provide much needed constraints on field processes

Small Shelly Fossil Preservation and the Role of Early Diagenetic Redox in the Early Triassic

Minute fossils from a variety of different metazoan clades, collectively referred to as small shelly fossils, represent a distinctive taphonomic mode that is most commonly reported from the Cambrian Period. Lower Triassic successions of the western United States, deposited in the aftermath of the end-Permian mass extinction, provide an example of small shelly style preservation that significantly post-dates Cambrian occurrences. Glauconitized and phosphatized echinoderms and gastropods are preserved in the insoluble residues of carbonates from the Virgin Limestone Member of the Moenkopi Formation. Echinoderm plates, spines and other skeletal elements are preserved as stereomic molds; gastropods are preserved as steinkerns. All small shelly style fossils are preserved in the small size fractions of the residues (177 to 420 lm), which is consistent with the size selection of small shelly fossils in the Cambrian. Energy-dispersive X-ray spectra of individual fossils coupled with X-ray diffraction of residues confirm that the fossils are dominantly preserved by apatite and glauconite, and sometimes a combination of the two minerals. The nucleation of both of these minerals requires that pore water redox oscillated between oxic and anoxic conditions, which, in turn, implies that Lower Triassic carbonates periodically experienced oxygen depletion after deposition and during early diagenesis. Long-term oxygen depletion persisted through the Early Triassic, creating diagenetic conditions that were instrumental in the preservation of small shelly fossils in Triassic and, likely, Paleozoic examples

Humidity-induced phase transitions of ferric sulfate minerals studied by in situ and ex situ X-ray diffraction

Phases encountered in the hydration of monoclinic and trigonal anhydrous Fe2(SO4)3 and evaporation of Fe2(SO4)3 solutions at room temperature were determined using in situ and ex situ X-ray diffraction (XRD) under dynamic relative humidity (RH) control at room temperature (22–25 °C). Both monoclinic and trigonal forms of Fe2(SO4)3 remain anhydrous at 11% RH or below, and undergo the following phase evolution sequence: anhydrous Fe2(SO4)3 → (ferricopiapite, rhomboclase) → kornelite → paracoquimbite at RH between 33 and 53% as a function of time. Evaporation of aqueous Fe2(SO4)3 solutions at 40% < RH < 60% results in precipitation of ferricopiapite and rhomboclase during evaporation, followed by a transition to kornelite and then paracoquimbite. Evaporation at RH < 33% produced an amorphous ferric-sulfate phase. The presence of some iron sulfate hydrates and their stability under varying RH are not only determined by the final humidity level, but also the intermediate stages and hydration history (i.e., either ferricopiapite or paracoquimbite can be a stable phase at 62% RH depending on the hydration history). The sensitivity to humidity change and path-dependent transitions of ferric sulfates make them potentially valuable indicators of paleo-environmental conditions and past water activity on Mars. The phase relationships reported herein can help in understanding the diagenesis of ferric sulfate minerals, and are applicable to geochemical modeling of mineral solubility in multi-component systems, an endeavor hindered by the need for fundamental laboratory studies of iron sulfate hydrates

Tropical biomass burning smoke plume size, shape, reflectance, and age based on 2001–2009 MISR imagery of Borneo

Land clearing for crops, plantations and grazing results in anthropogenic burning of tropical forests and peatlands in Indonesia, where images of fire-generated aerosol plumes have been captured by the Multi-angle Imaging SpectroRadiometer (MISR) since 2001. Here we analyze the size, shape, optical properties, and age of distinct fire-generated plumes in Borneo from 2001–2009. The local MISR overpass at 10:30 a.m. misses the afternoon peak of Borneo fire emissions, and may preferentially sample longer plumes from persistent fires burning overnight. Typically the smoke flows with the prevailing southeasterly surface winds at 3–4 m s&lt;sup&gt;−1&lt;/sup&gt;, and forms ovoid plumes whose mean length, height, and cross-plume width are 41 km, 708 m, and 27% of the plume length, respectively. 50% of these plumes have length between 24 and 50 km, height between 523 and 993 m and width between 18% and 30% of plume length. Length and cross-plume width are lognormally distributed, while height follows a normal distribution. Borneo smoke plume heights are similar to previously reported plume heights, yet Borneo plumes are on average nearly three times longer than previously studied plumes. This could be due to sampling or to more persistent fires and greater fuel loads in peatlands than in other tropical forests. Plume area (median 169 km&lt;sup&gt;2&lt;/sup&gt;, with 25th and 75th percentiles at 99 km&lt;sup&gt;2&lt;/sup&gt; and 304 km&lt;sup&gt;2&lt;/sup&gt;, respectively) varies exponentially with length, though for most plumes a linear relation provides a good approximation. The MISR-estimated plume optical properties involve greater uncertainties than the geometric properties, and show patterns consistent with smoke aging. Optical depth increases by 15–25% in the down-plume direction, consistent with hygroscopic growth and nucleation overwhelming the effects of particle dispersion. Both particle single-scattering albedo and top-of-atmosphere reflectance peak about halfway down-plume, at values about 3% and 10% greater than at the origin, respectively. The initially oblong plumes become brighter and more circular with time, increasingly resembling smoke clouds. Wind speed does not explain a significant fraction of the variation in plume geometry. We provide a parameterization of plume shape that can help atmospheric models estimate the effects of plumes on weather, climate, and air quality. Plume age, the age of smoke furthest down-plume, is lognormally distributed with a median of 2.8 h (25th and 75th percentiles at 1.3 h and 4.0 h), different from the median ages reported in other studies. Intercomparison of our results with previous studies shows that the shape, height, optical depth, and lifetime characteristics reported for tropical biomass burning plumes on three continents are dissimilar and distinct from the same characteristics of non-tropical wildfire plumes

Do biomass burning aerosols intensify drought in equatorial Asia during El Niño?

During El Niño years, fires in tropical forests and peatlands in equatorial Asia create large regional smoke clouds. We characterized the sensitivity of these clouds to regional drought, and we investigated their effects on climate by using an atmospheric general circulation model. Satellite observations during 2000–2006 indicated that El Niño-induced regional drought led to increases in fire emissions and, consequently, increases in aerosol optical depths over Sumatra, Borneo and the surrounding ocean. Next, we used the Community Atmosphere Model (CAM) to investigate how climate responded to this forcing. We conducted two 30 year simulations in which monthly fire emissions were prescribed for either a high (El Niño, 1997) or low (La Niña, 2000) fire year using a satellite-derived time series of fire emissions. Our simulations included the direct and semi-direct effects of aerosols on the radiation budget within the model. We assessed the radiative and climate effects of anthropogenic fire by analyzing the differences between the high and low fire simulations. Fire aerosols reduced net shortwave radiation at the surface during August–October by 19.1&amp;plusmn;12.9 W m&lt;sup&gt;&amp;minus;2&lt;/sup&gt; (10%) in a region that encompassed most of Sumatra and Borneo (90&amp;deg; E–120&amp;deg; E, 5&amp;deg; S–5&amp;deg; N). The reductions in net shortwave radiation cooled sea surface temperatures (SSTs) and land surface temperatures by 0.5&amp;plusmn;0.3 and 0.4&amp;plusmn;0.2 &amp;deg;C during these months. Tropospheric heating from black carbon (BC) absorption averaged 20.5&amp;plusmn;9.3 W m&lt;sup&gt;&amp;minus;2&lt;/sup&gt; and was balanced by a reduction in latent heating. The combination of decreased SSTs and increased atmospheric heating reduced regional precipitation by 0.9&amp;plusmn;0.6 mm d&lt;sup&gt;&amp;minus;1&lt;/sup&gt; (10%). The vulnerability of ecosystems to fire was enhanced because the decreases in precipitation exceeded those for evapotranspiration. Together, the satellite and modeling results imply a possible positive feedback loop in which anthropogenic burning in the region intensifies drought stress during El Niño

Clay mineralogy, strontium and neodymium isotope ratios in the sediments of two High Arctic catchments (Svalbard)

he identification of sediment sources to the ocean is a prerequisite to using marine sediment cores to extract information on past climate and ocean circulation. Sr and Nd isotopes are classical tools with which to trace source provenance. Despite considerable interest in the Arctic Ocean, the circum-Arctic source regions are poorly characterised in terms of their Sr and Nd isotopic compositions. In this study we present Sr and Nd isotope data from the Paleogene Central Basin sediments of Svalbard, including the first published data of stream suspended sediments from Svalbard. The stream suspended sediments exhibit considerable isotopic variation (εNd = −20.6 to −13.4; 87Sr ∕ 86Sr = 0.73421 to 0.74704) which can be related to the depositional history of the sedimentary formations from which they are derived. In combination with analysis of the clay mineralogy of catchment rocks and sediments, we suggest that the Central Basin sedimentary rocks were derived from two sources. One source is Proterozoic sediments derived from Greenlandic basement rocks which are rich in illite and have high 87Sr ∕ 86Sr and low εNd values. The second source is Carboniferous to Jurassic sediments derived from Siberian basalts which are rich in smectite and have low 87Sr ∕ 86Sr and high εNd values. Due to a change in depositional conditions throughout the Paleogene (from deep sea to continental) the relative proportions of these two sources vary in the Central Basin formations. The modern stream suspended sediment isotopic composition is then controlled by modern processes, in particular glaciation, which determines the present-day exposure of the formations and therefore the relative contribution of each formation to the stream suspended sediment load. This study demonstrates that the Nd isotopic composition of stream suspended sediments exhibits seasonal variation, which likely mirrors longer-term hydrological changes, with implications for source provenance studies based on fixed end-members through time

The TOSCA Registry for Tuberous Sclerosis-Lessons Learnt for Future Registry Development in Rare and Complex Diseases.

Introduction: The TuberOus SClerosis registry to increase disease Awareness (TOSCA) is an international disease registry designed to provide insights into the clinical characteristics of patients with Tuberous Sclerosis Complex (TSC). The aims of this study were to identify issues that arose during the design, execution, and publication phases of TOSCA, and to reflect on lessons learnt that may guide future registries in rare and complex diseases. Methods: A questionnaire was designed to identify the strengths, weaknesses, and issues that arose at any stage of development and implementation of the TOSCA registry. The questionnaire contained 225 questions distributed in 7 sections (identification of issues during registry planning, during the operation of the registry, during data analysis, during the publication of the results, other issues, assessment of lessons learnt, and additional comments), and was sent by e-mail to 511 people involved in the registry, including 28 members of the Scientific Advisory Board (SAB), 162 principal investigators (PIs), and 321 employees of the sponsor belonging to the medical department or that were clinical research associate (CRA). Questionnaires received within the 2 months from the initial mailing were included in the analysis. Results: A total of 53 (10.4%) questionnaires were received (64.3% for SAB members, 12.3% for PIs and 4.7% for employees of the sponsor), and the overall completeness rate for closed questions was 87.6%. The most common issues identified were the limited duration of the registry (38%) and issues related to handling of missing data (32%). In addition, 25% of the respondents commented that biases might have compromised the validity of the results. More than 80% of the respondents reported that the registry improved the knowledge on the natural history and manifestations of TSC, increased disease awareness and helped to identify relevant information for clinical research in TSC. Conclusions: This analysis shows the importance of registries as a powerful tool to increase disease awareness, to produce real-world evidence, and to generate questions for future research. However, there is a need to implement strategies to ensure patient retention and long-term sustainability of patient registries, to improve data quality, and to reduce biases

Analysis of Energy Flow in US GLOBEC Ecosystems Using End-to-End Models

End-to-end models were constructed to examine and compare the trophic structure and energy flow in coastal shelf ecosystems of four US Global Ocean Ecosystem Dynamics (GLOBEC) study regions: the Northern California Current, the Central Gulf of Alaska, Georges Bank, and the Southwestern Antarctic Peninsula. High-quality data collected on system components and processes over the life of the program were used as input to the models. Although the US GLOBEC program was species-centric, focused on the study of a selected set of target species of ecological or economic importance, we took a broader community-level approach to describe end-to-end energy flow, from nutrient input to fishery production. We built four end-to-end models that were structured similarly in terms of functional group composition and time scale. The models were used to identify the mid-trophic level groups that place the greatest demand on lower trophic level production while providing the greatest support to higher trophic level production. In general, euphausiids and planktivorous forage fishes were the critical energy-transfer nodes; however, some differences between ecosystems are apparent. For example, squid provide an important alternative energy pathway to forage fish, moderating the effects of changes to forage fish abundance in scenario analyses in the Central Gulf of Alaska. In the Northern California Current, large scyphozoan jellyfish are important consumers of plankton production, but can divert energy from the rest of the food web when abundant