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.     

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.     

Relative abundance, age, growth, and fecundity of grubby Myoxocephalus aenaeus in Niantic River and Niantic Bay, Long Island Sound

Grubby (Myoxocephalus aenaeus, Cottidae) is a common benthic fish of inshore waters and estuaries of eastern Long Island Sound; however, little information exists on their life history or population demographics. This study utilised a long-term data series (1976–2002) to assess grubby life history and population demographics and explores trends in the Niantic River and Niantic Bay populations. In addition, we examined the age, size, and fecundity of adult grubby in 2001–02 to determine the population characteristics in the region. Mean grubby catch per unit effort (CPUE) in Niantic Bay ranged from 0.4 per trawl in 1976 to 2.9 per trawl in 1984 while river CPUE ranged from 0.4 per trawl in 1977 to 7.6 per trawl in 1989. Catch of grubby in bottom trawls varied seasonally with highest CPUE occurring in winter. Highest entrainment of grubby larvae occurred in 2001 while the lowest entrainment observed was in 1991. Four age classes, 0+ through III+, were derived from otolith analysis (N = 51) although length frequency analysis suggested the possibility of older fish in the population. The total number of eggs in ovaries ranged from 286 to 16 451 for grubby (N = 64) between 52 mm and 155 mm TL. Results of this study indicated a decline in abundance of adult grubby over the 26-year period, possibly related to concurrent declines in eelgrass (Zostera marina) abundance and/or increased water temperature.     

Use of suppressive subtractive hybridization and cDNA arrays to discover patterns of altered gene expression in the liver of dihydrotestosterone and 11-ketotestosterone exposed adult male largemouth bass (Micropterus salmoides)

In this study male largemouth bass (LMB) were exposed to the naturally occurring androgens, dihydrotestosterone (DHT) or 11-ketotestosterone (11-KT) in order to identify genes that are differentially regulated by these steroid hormones. Using subtractive hybridization on livers of fish treated with DHT against vehicle control, many novel LMB genes were cloned. These genes were added to our gene library and arrayed. Six genes were up-regulated and five were down-regulated by both androgens. But, each androgen also regulated specific genes. One gene that was identified as a potential androgen marker was spermidine-spermine-N(1)-acetyltransferase that was up-regulated by both androgens. Determining which genes are responsive to natural androgens will help to identify biochemical pathways that are impacted.     

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.     

Phytoplankton and iron: validation of a global three-dimensional ocean biogeochemical model

The JGOFS program and NASA ocean-color satellites have provided a wealth of data that can be used to test and validate models of ocean biogeochemistry. A coupled three-dimensional general circulation, biogeochemical, and radiative model of the global oceans was validated using these in situ data sources and satellite data sets. Biogeochemical processes in the model were determined from the influences of circulation and turbulence dynamics, irradiance availability, and the interactions among four phytoplankton functional groups (diatoms, chlorophytes, cyanobacteria, and coccolithophores) and four nutrients (nitrate, ammonium, silica, and dissolved iron).Annual mean log-transformed dissolved iron concentrations in the model were statistically positively correlated on basin scale with observations (P<0.05) over the eight (out of 12) major oceanographic basins where data were available. The model tended to overestimate in situ observations, except in the Antarctic where a large underestimate occurred. Inadequate scavenging and excessive remineralization and/or regeneration were possible reasons for the overestimation.Basin scale model chlorophyll seasonal distributions were positively correlated with SeaWiFS chlorophyll in each of the 12 oceanographic basins (P<0.05). The global mean difference was 3.9% (model higher than SeaWiFS).The four phytoplankton groups were initialized as homogeneous and equal distributions throughout the model domain. After 26 years of simulation, they arrived at reasonable distributions throughout the global oceans: diatoms predominated high latitudes, coastal, and equatorial upwelling areas, cyanobacteria predominated the mid-ocean gyres, and chlorophytes and coccolithophores represented transitional assemblages. Seasonal patterns exhibited a range of relative responses: from a seasonal succession in the North Atlantic with coccolithophores replacing diatoms as the dominant group in mid-summer, to successional patterns with cyanobacteria replacing diatoms in mid-summer in the central North Pacific. Diatoms were associated with regions where nutrient availability was high. Cyanobacteria predominated in quiescent regions with low nutrients.While the overall patterns of phytoplankton functional group distributions exhibited broad qualitative agreement with in situ data, quantitative comparisons were mixed. Three of the four phytoplankton groups exhibited statistically significant correspondence across basins. Diatoms did not. Some basins exhibited excellent correspondence, while most showed moderate agreement, with two functional groups in agreement with data and the other two in disagreement. The results are encouraging for a first attempt at simulating functional groups in a global coupled three-dimensional model but many issues remain.     

Patterns and controls of surface sediment distribution: west-central Florida inner shelf

The west-central Florida inner shelf represents a transition between the quartz-dominated barrier-island system and the carbonate-dominated mid-outer shelf. Surface sediments exhibit a complex distribution pattern that can be attributed to multiple sediment sources and the ineffectiveness of physical processes for large-scale sediment redistribution. The west Florida shelf is the submerged extension of the Florida carbonate platform, consisting of a limestone karst surface veneered with a thin unconsolidated sediment cover. A total of 498 surface sediment samples were collected on the inner shelf and analyzed for texture and composition. Results show that sediment consists of a combination of fine quartz sand and coarse, biogenic carbonate sand and gravel, with variable but subordinate amounts of black, phosphorite-rich sand. The carbonate component consists primarily of molluskan fragments. The distribution is patchy and discontinuous with no discernible pattern, and the transition between sediment types is generally abrupt. Quartz-rich sediment dominates the inner 15 km north of the entrance into Tampa Bay, but south of the Bay is common only along the inner 3 km. Elsewhere, carbonate-rich sediment is the predominate sediment type, except where there is little sediment cover, in which cases black, phosphorite-rich sand dominates. Sediment sources are likely within, or around the periphery of the basin. Fine quartz sand is likely reworked from coastal units deposited during Pleistocene sea-level high stands. Carbonate sand and gravel is produced by marine organisms within the depositional basin. The black, phosphorite-rich sand likely originates from the bioerosion and reworking of the underlying strata that irregularly crop out within the study area. The distribution pattern contains elements of both storm- and tide-dominated siliciclastic shelves, but it is dictated primarily by the sediment source, similar to some carbonate systems. Other systems with similar sediment attributes include cool-water carbonate, sediment-starved, and mixed carbonate/siliciclastic systems. This study suggests a possible genetic link among the three systems.     

Diffusion-limited REE uptake by eclogite garnets and its consequences for Lu–Hf and Sm–Nd geochronology

Garnets from the Zermatt-Saas Fee eclogites contain narrow central peaks for Lu + Yb + Tm ± Er and at least one additional small peak towards the rim. The REE Sm + Eu + Gd + Tb ± Dy are depleted in the cores but show one prominent peak close to the rim. These patterns cannot be modeled using Rayleigh fractionation accompanied by mineral breakdown reactions. Instead, the patterns are well explained using a transient matrix diffusion model where REE uptake is limited by diffusion in the matrix surrounding the porphyroblast. Observed profiles are well matched if a roughly linear radius growth rate is used. The secondary peaks in the garnet profiles are interpreted to reflect thermally activated diffusion due to temperature increase during prograde metamorphism. The model predicts anomalously low ¹⁷⁶Lu/¹⁷⁷Hf and ¹⁴⁷Sm/¹⁴⁴Nd ratios in garnets where growth rates are fast compared to diffusion of the REE, and these results have important implications for Lu–Hf and Sm–Nd geochronology using garnet.