Ce(III) and Ce(IV) (re)distribution and fractionation in a laterite profile from Madagascar: Insights from in situ XANES spectroscopy at the Ce LIII-edge

The distribution of trivalent and tetravalent cerium, Ce(III) and Ce(IV) respectively, in a lateritic profile from Madagascar, has been characterized by X-ray-absorption near-edge structure (XANES) spectroscopy at the Ce LIII-edge on the LUCIA beamline (SOLEIL synchrotron, France). XANES spectra were acquired on bulk-rock samples as well as on specific lateritic minerals or polymineral zones (in-situ measurements) of the tonalite bedrock and the three overlying weathered horizons (C-, B- and A-horizons). Geochemically, the bedrock, and the A- and C-horizons show similar rare earth element content (REE = 363–405 mg/kg). They also display the same positive Ce-anomaly (CeCN/Ce∗ = 1.12–1.45), which is therefore likely to be inherited from the bedrock. In the B-horizon, the higher REE content (REE = 2194 mg/kg) and the larger Ce-anomaly (CeCN/Ce∗ = 4.26) are consistent with an accumulation zone caused by the evaporation of groundwater during the dry season. There is a good agreement between the Ce(III)/Cetotal ratio (XCe(III)) deduced from the positive Ce-anomaly (bulk-rock geochemical data) and that derived from XANES spectroscopy on the same bulk-rock samples (BR-XCe(III)-XANES) in the bedrock, and the C- and B-horizons. In the A-horizon, XANES measurements on bulk rock and minerals revealed a higher BR-XCe(III)-XANES (up to 100%) compared to the XCe(III) deduced from geochemical data (XCe(III) = 79%). The preservation of a positive Ce-anomaly in the A-horizon suggests that the Ce mobilization and redistribution during weathering occurred with no significant Ce fractionation from other trivalent REE. Remarkably, the only investigated sample where cerianite is observed belongs to the B-horizon. Within this horizon, Ce oxidation state varies depending on the microstructural position (porosity, cracks, clay-rich groundmass). The highest Ce(IV) concentrations are measured in cerianite (and aluminophosphates) localized in pores at the vicinity of Mn-rich domains (XCe(III)-XANES = 30–51%). Therefore, Ce fractionation from other REE is attributed to a Ce oxidation and precipitation potentially assisted by oxyhydroxide scavenging. In the C-horizon, Ce(III) and Ce(IV) are mainly distributed in REE-minerals of the rhabdophane group found in pores and cracks. The similarity between the Ce(III) proportion of rhabdophane grains (XCe(III)-XANES = 74–89%) with that of the bedrock (BR-XCe(III)-XANES = 79%) suggests no significant fractionation of Ce(III) and Ce(IV) between solution and mineral during the successive stages of primary REE-mineral alteration, transport in solution and secondary precipitation in the incipient stages of weathering. Overall, our novel spectroscopic approach shows that Ce is not necessarily oxidized nor fractionated from other REE during weathering in lateritic conditions. This implies that like Ce(III), Ce(IV) can be mobilized in aqueous fluids during weathering, possibly thanks to complexation with organic molecules, and can precipitate together with Ce(III) in secondary REE-bearing minerals. The corollary is that (paleo)redox reconstructions in soils and/or sediments based on Ce-anomaly in weathered rocks or minerals must be interpreted with caution.

Benchmarking the simulation of Cr isotope fractionation

A benchmark problem set consisting of four problem levels was developed for the simulation of Cr isotope fractionation in 1D and 2D domains. The benchmark is based on a recent field study where Cr(VI) reduction and accompanying Cr isotope fractionation occurs abiotically by an aqueous reaction with dissolved Fe 2+ (Wanner et al., 2012., Appl. Geochem., 27, 644–662). The problem set includes simulation of the major processes affecting the Cr isotopic composition such as the dissolution of various Cr(VI) bearing minerals, fractionation during abiotic aqueous Cr(VI) reduction, and non-fractionating precipitation of Cr(III) as sparingly soluble Cr-hydroxide. Accuracy of the presented solutions was ensured by running the problems with four well-established reactive transport modeling codes: TOUGHREACT, MIN3P, CRUNCHFLOW, and FLOTRAN. Results were also compared with an analytical Rayleigh-type fractionation model. An additional constraint on the correctness of the results was obtained by comparing output from the problem levels simulating Cr isotope fractionation with the corresponding ones only simulating bulk concentrations. For all problem levels, model to model comparisons showed excellent agreement, suggesting that for the tested geochemical processes any code is capable of accurately simulating the fate of individual Cr isotopes.

TIMS measurements of full range of natural Ca isotopes with internally consistent fractionation correction

This study presents static measurements of the Ca isotopic composition of standard reference materials SRM 915 a/b on a Triton Plus™ thermal ionization mass spectrometer with a specially developed Faraday cup array allowing simultaneous measurement of 40Ca and 48Ca. The total amount of Ca in all analyses was kept < 1 µg. With this setup the measurement uncertainties were 0.06 ‰ for 40Ca/44Ca and 0.12 ‰ for 48Ca/40Ca. Measuring all isotopes simultaneously better allows to test the internal consistency of different Ca isotope abundances reported in the literature. The exponential law was observed to correct incompletely instrumental mass fractionation. An improved fractionation correction based on the exponential law is proposed. It changes the 40Ca/44Ca ratio of SRM 915a (corrected relative to 42Ca/44Ca = 0.31221; 48Ca/44Ca = 0.08871) from 47.1635 ± 0.0028 to 47.1649 ± 0.0047. The measurements of SRM 915b were performed with different analytical conditions (runs were prolonged till complete filament load depletion). Even if the 40Ca/44Ca ratio of SRM 915b, when corrected with the simple exponential law, appears different (47.1532 ± 0.0038) from that of SRM 915a, it becomes coincident (47.1613 ± 0.0028) when corrected with a second-order refinement. This supports the use of the improved exponential law to obtain internally consistent Ca isotope ratio for natural samples.

Constraints on barium isotope fractionation during aragonite precipitation by corals

We present a barium (Ba) isotope fractionation study of marine biogenic carbonates (aragonitic corals). The major aim is to provide first constraints on the Ba isotope fractionation between modern surface sea water and coral skele- ton. Mediterranean surface sea water was found to be enriched in the heavy Ba isotopes compared to previously reported values for marine open ocean authi- genic and terrestrial minerals. In aquarium experiments with a continuous sup- ply of Mediterranean surface water, the Ba isotopic composition of the bulk sample originating from cultured, aragonitic scleractinian corals (d137/134Ba between +0.16 +/- 0.12permil and +0.41 +/-0.12permil) were isotopically identical or lighter than that of the ambient Mediterranean surface sea water (d137/134Ba = +0.42 +/- 0.07permil, 2SD), which corresponds to an empirical maximum value of Ba isotope fractionation of D137/134Bacoral-seawater = -0.26 +/- 0.14permil at 25°C. This maximum Ba isotope fractionation is close and identical in direction to previous results from inorganic precipitation experiments with aragonite- structured pure BaCO3 (witherite). The variability in measured Ba concentrations of the cultured corals is at odds with a uniform distribution coefficient, DBa/Ca, thus indicating stronger vital effects on isotope than element discrimination. This observation supports the hypothesis that the Ba isotopic compositions of these corals do not result from simple equilibrium between the skeleton and the bulk sea water. Complementary coral samples from natural settings (tropical shallow-water corals from the Bahamas and Florida and cold- water corals from the Norwegian continental shelf) show an even wider range in d137/134Ba values (+0.14 +/- 0.08permil and +0.77 +/- 0.11permil), most probably due to additional spatial and/or temporal sea water heterogeneity, as indicated by recent publications.

A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee, Switzerland

In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ18O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in 18O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO32−] (∼50 μmol/l) in the surface waters. The resulting weighted average δ18O value for the studied period is −9.6‰, compared with a calculated equilibrium δ18O value of −9.4‰. These data convincingly demonstrate that δ18O of calcite are, for the most part, a very reliable proxy for temperature and δ18O of the water.

The Emergency Department: Rising wait times, costs, and possible remedies

Emergency Departments (EDs) and Emergency Rooms (ERs) are designed to manage trauma, respond to disasters, and serve as the initial care for those with serious illnesses. However, because of many factors, the ED has become the doorway to the hospital and a “catch-all net” for patients including those with non-urgent needs. This increase in the population in the ED has lead to an increase in wait times for patients. It has been well documented that there has been a constant and consistent rise in the number of patients that frequent the ED (National Center for Health Statistics, 2002); the wait time for patients in the ED has increased (Pitts, Niska, Xu, & Burt, 2008); and the cost of the treatment in the ER has risen (Everett Clinic, 2008). Because the ED was designed to treat patients who need quick diagnoses and may be in potential life-threatening circumstances, management of time can be the ultimate enemy. If a system was implemented to decrease wait times in the ED, decrease the use of ED resources, and decrease costs endured by patients seeking care, better outcomes for patients and patient satisfaction could be achieved. The goal of this research was to explore potential changes and/or alternatives to relieve the burden endured by the ED. In order to explore these options, data was collected by conducting one-on-one interviews with seven physicians closely tied to a Level 1 ED (Emergency Room physicians, Trauma Surgeons and Primary Care physicians). A qualitative analysis was performed on the responses of one-on-one interviews with the aforementioned physicians. The interviews were standardized, open-ended questions that probe what makes an effective ED, possible solutions to improving patient care in the ED, potential remedies for the mounting problems that plague the ED, and the feasibility of bringing Primary Care Physicians to the ED to decrease the wait times experienced by the patient. From the responses, it is clear that there needs to be more research in this area, several areas need to be addressed, and a variety of solutions could be implemented. The most viable option seems to be making the ED its own entity (similar to the clinic or hospital) that includes urgent clinics as a part of the system, in which triage and better staffing would be the most integral part of its success.^

SYSTEMIC TOXICITY IN RODENTS FOLLOWING ACUTE AND SUBCHRONIC INHALATION OF FORMALDEHYDE (FLOW CYTOMETRY, CELL CYCLE KINETICS, ALKALINE ELUTION)

Systemic toxicity was evaluated in Sprague-Dawley (SD) rats and A-strain mice exposed to HCHO inhalation at 0, 0.5, 3, or 15 ppm for six hours/day, five days/week for up to 24 weeks. Toxicity was measured by flow cytometry to detect changes in cell cycle RNA and DNA content and by alkaline elution to detect DNA protein cross-link (DPC) formation.^ A G(,2)M block was detected in SD rat marrow following one week of exposure to 0.5, 3, or 15 ppm HCHO, but this block did not persist. No effect was noticed in mouse marrow. Only a minimal increase in RNA content was detected in rat or mouse marrow while exfoliated lung cells showed a significant increase in RNA activity after one week of exposure.^ Acute exposure in SD rats for four hours/day for one or three days at 150 ppm showed an increase in RNA activity in exfoliated lung cells but not in the marrow after one day. On the third day, dead cells were detected in exfoliated lung cells.^ In alkaline elution studies, no DPC were detected in marrow of SD rats after 24 weeks exposure up to 15 ppm. During acute exposures, a dose response relationship was detected in SD rat exfoliated lung cells which yielded cross-linking factors of 0.954, 1.237, and 1.417 following a four hour exposure to 15, 50, or 150 ppm, respectively. No DPC were detected in the marrow at 150 ppm. In vitro exposures to HCHO of CHO and SHE cells and rat marrow cells revealed the production of DPC and DNA-DNA cross-links.^ Cytoxan treatment of SD rats was used to provide positive controls for flow cytometry and alkaline elution. A drastic reduction in RNA content and cycling cells occurred one day following treatment. After four days, RNA content was greatly increased; and on day eleven the marrow had regenerated. DPCs were detected in both the marrow and the exfoliated lung cells.^ The lack of significant responses in SD rats and A-strain mice below 15 ppm HCHO is explainable by host defense mechanisms. Apparently, the mucociliary apparatus and enzymatic detoxification are sufficient to reduce systemic toxicity to low level concentrations of formaldehyde. ^

(Table 2) Chemical composition of quenched glasses from the Mohns and Knipovich Ridges

The aim of this project was a petrogeochemical study of igneous rocks in the areas of the Mohns and Knipovich Ridges, both being the northern extensions of the Mid-Atlantic Ridge (MAR), using data available for quenching glass samples collected during Cruises 36 and 38 of R/V Akademic Mstislav Keldysh and during Cruise 15 of R/V Professor Logachev. Results of igneous rock studying from the Mohns and Knipovich Ridges at the background of evolution of the total North Atlantic Province, which had been identified earlier from tectonic and geophysical data, showed that igneous rocks of the Knipovich Ridge can be ranked as shallow tholeiites, primary melts of which were relatively rich in Na and Si and poor in Fe. This type of magma is characteristic of colder regions of the oceanic lithosphere. Its occurrence in the Knipovich Ridge and its potential propagation up to the Gakkel Ridge suggest that igneous rocks of this region originated under conditions of passive spreading in contrast to the MAR region in vicinity of Iceland and Azores, where substantial contribution of hotter material of a rising plume contributed to formation of the oceanic crust. The North Atlantic Ocean is the youngest province in terms of ocean-floor opening. Geologically and geophysically it is one of well studied regions of the World Ocean. Nevertheless some basic key items of its origin still remain to be clarified. In 1975 Scatler et al. proved specifics of this region manifested in growth of the gravity field, and also in relative height of the ocean floor in the region of 33-70°N, which was associated by them with rise of the hotter mantle, as compared with common regions of the Mid-Atlantic Ridge. Later this view was confirmed by character of magmatism, which differed in depth of generation and by melting degree of the resulting primary magma. Uniqueness of the North Atlantic region was also proved by the fact that this region was marked by extensive geochemical anomalies associated with Azores, Iceland, and Jan Mayen. All of these data allow to consider the northern part of the MAR (north of 33°N) as an united global geotectonic province. The Mohns and Knipovich Ridges located north of Iceland locate at the northern end of this province. This is the least known region. Therefore, new data for ridge areas of 73-77°N are needed for more complete geologic history of the Arctic Basin. The aim of this study was to carry out a complex comparison of magmatism at the Mohns and Knipovich Ridges with magmatism at large segments of the MAR northern province and to reconstruct mechanisms of primary magma formation, as well as conditions of their fractionation. This paper was based on results of studying quenched glasses, which reflect evolution of melt in the course of its formation.

Calcium isotope fractionation in cultured, modern and fossil scleractinian coral skeleton

The present study investigates the influence of environmental (temperature, salinity) and biological (growth rate, inter-generic variations) parameters on calcium isotope fractionation (d44/40Ca) in scleractinian coral skeleton to better constrain this record. Previous studies focused on the d44/40Ca record in different marine organisms to reconstruct seawater composition or temperature, but only few studies investigated corals. This study presents measurements performed on modern corals from natural environments (from the Maldives for modern and from Tahiti for fossil corals) as well as from laboratory cultures (Centre Scientifique de Monaco). Measurements on Porites sp., Acropora sp., Montipora verrucosa and Stylophora pistillata allow constraining inter-generic variability. Our results show that the fractionation of d44/40Ca ranges from 0.6 to 0.1 per mil, independent of the genus or the environmental conditions. No significant relationship between the rate of calcification and d44/40Ca was found. The weak temperature dependence reported in earlier studies is most probably not the only parameter that is responsible for the fractionation. Indeed, sub-seasonal temperature variations reconstructed by d18O and Sr/Ca ratio using a multi-proxy approach, are not mirrored in the coral's d44/40Ca variations. The intergeneric variability and intrageneric variability among the studied samples are weak except for S. pistillata, which shows calcium isotopic values increasing with salinity. The variability between samples cultured at a salinity of 40 is higher than those cultured at a salinity of 36 for this species. The present study reveals a strong biological control of the skeletal calcium isotope composition by the polyp and a weak influence of environmental factors, specifically temperature and salinity (except for S. pistillata). Vital effects have to be investigated in situ to better constrain their influence on the calcium isotopic signal. If vital effects could be extracted from the isotopic signal, the calcium isotopic composition of coral skeletons could provide reliable information on the calcium composition and budget in ocean.