The Fe-C system at 5 GPa and implications for Earth’s core

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.     

Comparison of cytochrome P450 in three butterflyfish species: Ecological implications of elevated CYP2B and CYP3A in Chaetodon capistratus

The relationship between cytochrome P450 and feeding on terpenoid-rich gorgonian corals was investigated in a species of tropical butterflyfish and compared with two other sympatric congeners that do not feed on gorgonians. Fish were collected from non-polluted waters in Belize and the levels of two cytochrome P450 isozymes (CYP2B and CYP3A) were immunoquantitated in addition to quantification of total P450. Chaetodon capistratus regularly feeds on gorgonian corals and has higher levels of total hepatic microsomal cytochrome P450 than C. ocellatus or C. striatus. The content of hepatic P450 (0.588–0.794 nmol mg⁻¹) in C. capistratus is among the highest ever reported in teleosts from non-polluted waters and is significantly greater than detected in C. ocellatus or C. striatus. Chaetodon capistratus also had a larger hepatic index (g liver per g fish) and more microsomal protein (mg protein per g liver), factors that translate into 3.3- to 8-fold more total P450 per g fish. Sexual differences in total P450 were observed between male and female C. capistratus, but not among the other species. The contents of proteins detected by immunoassay with polyclonal anti-scup P450B (CYP2B) and anti-human P4503A (CYP3A) were 2- to 10-fold and 2- to 20-fold greater, respectively, in C. capistratus than in the congeneric species. CYP2 and CYP3 gene families in mammals are thought to have evolved partially in response to dietary allelochemicals. These results suggest that these P450 isozymes may also be important in marine teleosts that feed on terpenoid-rich prey.     

ENSO impacts on salinity in Tampa Bay, Florida

Estuarine salinity distributions reflect a dynamic balance between the processes that control estuarine circulation. At seasonal and longer time scales, freshwater inputs into estuaries represent the primary control on salinity distribution and estuarine circulation. El Niño-Southern Oscillation (ENSO) conditions influence seasonal rainfall and stream discharge patterns in the Tampa Bay, Florida region. The resulting variability in freshwater input to Tampa Bay influences its seasonal salinity distribution. During El Niño events, ENSO sea surface temperature anomalies (SSTAs) are significantly and inversely correlated with salinity in the bay during winter and spring. These patterns reflect the elevated rainfall over the drainage basin and the resulting elevated stream discharge and runoff, which depress salinity levels. Spatially, the correlations are strongest at the head of the bay, especially in bay sections with long residence times. During La Niña conditions, significant inverse correlations between ENSO SSTAs and salinity occur during spring. Dry conditions and depressed stream discharge characterize La Niña winters and springs, and the higher salinity levels during La Niña springs reflect the lower freshwater input levels.     

Sulfur contents of the parental metallic cores of magmatic iron meteorites

Magmatic iron meteorites are thought to be samples of the central metallic cores of asteroid-sized parent bodies. Sulfur is believed to have been an important constituent of these parental cores, but due to the low solubility of S in solid metal, initial S-contents for the magmatic groups cannot be determined through direct measurements of the iron meteorites. However, experimental solid metal-liquid metal partition coefficients show a strong dependence on the S-content of the metallic liquid. Thus, by using the experimental partition coefficients to model the fractional crystallization trends within magmatic iron meteorite groups, the S-contents of the parental cores can be indirectly estimated. Modeling the Au, Ga, Ge, and Ir fractionations in four of the largest magmatic iron meteorite groups leads to best estimates for the S-contents of the parental cores of 12 ± 1.5 wt% for the IIIAB group, 17 ± 1.5 wt% for the IIAB group, and 1 ± 1 wt% for the IVB group. The IVA elemental fractionations are not adequately fit by a simple fractional crystallization model with a unique initial S-content. These S-content estimates are much higher than those recently inferred from crystallization models involving trapped melt. The discrepancy is due largely to the different partition coefficients that are used by the two models. When only partition coefficients that are consistent with the experimental data are used, the trapped melt model, and the low S-contents it advocates, cannot match the Ge and Ir fractionations that are observed in IIIAB iron meteorites.     

Ecosystem history of Mississippi River-influenced continental shelf revealed through preserved phytoplankton pigments

Pigments determined by high performance liquid chromatography (HPLC) provide useful information concerning water column and epibenthic plant and microbial communities in both extant communities and accumulated sediments in lakes, estuaries and the ocean. Chlorophyll and its degradation products provide an estimate of overall biomass, and carotenoid pigments provide taxonomic biomarkers of phytoplankton. We examined the pigments preserved in sediment cores from the Louisiana continental shelf adjacent to the outflow of the Mississippi River system to document changes in phytoplankton community composition, phytoplankton abundance, and conditions of hypoxia over time. Carbon accumulated in sediments from water depths of 20-60 m is primarily derived from marine phytoplankton and represents the history of phytoplankton communities in the overlying water. There is a general increase in chlorophyll a, pheopigments, zeaxanthin, fucoxanthin and most carotenoids over time, with the change gradual from 1955 to 1970, followed by a fairly steady increase to 1997. The highest chloropigment concentrations are in cores from areas more likely to be exposed to seasonal hypoxia. These indicate an increase in eutrophication in the form of greater diatom and cyanobacterial production, or a worsening of hypoxia, or both. This trend expanded westward along the Louisiana shelf in the 1990s.     

Stratigraphy of Pleistocene glaciations in the St Elias Mountains,southwest Yukon,Canada

At least five Middle to Late Pleistocene advances of the northern Cordilleran Ice Sheet are preserved at Silver Creek, on the northeastern edge of the St Elias Mountains in southwest Yukon, Canada. Silver Creek is located 100 km up‐ice of the Marine Isotope Stage (MIS) 2 McConnell glacial limit of the St Elias lobe. This site contains ~3 km of nearly continuous lateral exposure of glacial and non‐glacial sediments, including multiple tills separated by thick gravel, loess and tilted lake beds. Infrared‐stimulated luminescence (IRSL) and AMS radiocarbon dating constrain the glacial deposits to MIS 2, 4, either MIS 6 or mid‐MIS 7, and two older Middle Pleistocene advances. This chronology and the tilt of the lake beds suggest Pleistocene uplift rates of up to 1.9 mm a^?1 along the Denali Fault since MIS 7. The non‐glacial sediment consists of sand, gravel, loess and organic beds from MIS 7, MIS 3 and the early Holocene. The MIS 3 deposits date to between 30–36 ¹⁴C ka BP, making Silver Creek one of the few well‐constrained MIS 3‐aged sites in Yukon. This confirms that ice receded close to modern limits in MIS 3. Pollen and macrofossil analyses show that a meadow‐tundra to steppe‐tundra mosaic with abundant herbs and forbs and few shrubs or trees, dominated the environment at this time. The stratigraphy at Silver Creek provides a palaeoclimatic record since at least MIS 8 and comprises the oldest direct record of Pleistocene glaciation in southwest Yukon.     

Hydrologic and water isotope characterization of a regulated Canadian Shield river basin

Stable water isotope surveys have increasingly been integrated into river basins studies, but fewer have used them to evaluate impact of hydropower regulation. This study applies hydrologic and water isotope survey approaches to a Canadian Shield river basin with both regulated and natural flows. Historical streamflow records were used to evaluate the influence of three hydroelectric reservoirs and unregulated portions of the basin on downstream flows and changes in water level management implemented after an extreme flood year (1979). In 2013, water isotope surveys of surface and source waters (e.g., rainfall, groundwater, snowmelt) were conducted to examine spatial and temporal variation in contributions to river flow. Seasonal changes in relative groundwater contribution were assessed using a water‐isotope mass balance approach. Within the basin, two regulated reservoirs exhibited inverted hydrographs with augmented winter flows, whereas a third exhibited a hydrograph dominated by spring snowmelt. In 2013, spatial variation in rain‐on‐snow and air temperatures resulted in a critical lag in snowmelt initiation in the southern and northern portions of the basin resulting in a dispersed, double peak spring hydrograph, contrasting with 1979 when a combination of rain‐on‐snow and coincident snowmelt led to the highest flood on record. Although eastern basin reservoirs become seasonally enriched in δ¹⁸O and δ²H values, unregulated western basin flows remain less variable due to groundwater driven baseflow with increasing influence downstream. Combined analysis of historical streamflow (e.g., flood of 1979, drought of 2010) and the 2013 water isotope surveys illustrate extreme meteorological conditions that current management activities are unable to prevent. In this study, the influence of evaporative fractionation on large surface water reservoirs provides important evidence of streamflow partitioning, illustrating the value of stable water isotope tracers for study of larger catchments.     

Experimental partitioning of trace elements into schreibersite with applications to IIG iron meteorites

Some of the defining characteristics of the IIG iron meteorite group are their high bulk P contents and massive, coarse schreibersite, which have been calculated to make up roughly 11–14 wt% of each specimen. In this study, we produced two data sets to investigate the formation of schreibersites in IIG irons: measurements of trace elements in the IIG iron meteorite Twannberg and experimental determinations of trace element partitioning into schreibersite. The schreibersite‐bearing experiments were conducted with schreibersite in equilibrium with a P‐rich melt and with bulk Ni contents ranging from 0 to 40 wt%. The partitioning behavior for the 20 elements measured in this study did not vary with Ni content. Comparison of the Twannberg measurements with the experimental results required a correction factor to account for the fact that the experiments were conducted in a simplified system that did not contain a solid metal phase. Previously determined solid metal/P‐rich melt partition coefficients were applied to infer schreibersite/solid metal partitioning behavior from the experiments, and once this correction was applied, the two data sets showed broad similarities between the schreibersite/solid metal distribution of elements. However, there were also differences noted, in particular between the Ni and P contents of the solid metal relative to the schreibersite inferred from the experiments compared to that measured in the Twannberg sample. These differences support previous interpretations that subsolidus schreibersite evolution has strongly influenced the Ni and P content now present in the solid metal phase of IIG irons. Quantitative attempts to match the IIG solid metal composition to that of late‐stage IIAB irons through subsolidus schreibersite growth were not successful, but qualitatively, this study corroborates the striking similarities between the IIAB and IIG groups, which are highly suggestive of a possible genetic link between the groups as has been previously proposed.