Se Abundances Research Articles

Factors controlling accumulation and bioavailability of selenium in paddy soils: A case study in Luxi County, China

Selenium (Se) accumulation in rice (Oryza sativa L.) has become a major global concern. Se offers multiple health benefits in humans; however, its inadequate or excessive intake can be harmful. Therefore, determining the factors driving Se abundance and bioavailability in paddy soils is essential to ensure the safety of human Se intake. This study investigated the accumulation, bioavailability, and distribution of Se in 820 paddy soil and rice grain samples from Luxi County, China to assess how soil properties (soil organic matter [SOM], cation exchange capacity [CEC], and pH), geographical factors (parent materials, elevation, and mean annual precipitation [MAP] and temperature [MAT]), and essential micronutrients (copper [Cu], zinc [Zn], and manganese [Mn]) govern Se accumulation and bioavailability in paddy soils. Results showed that the average soil Se content was 0.36 mg kg−1, which was higher than that in China (0.29 mg kg−1). Alternatively, the average rice grain Se content was 0.032 mg kg−1, which was lower than the minimum allowable content in Se-rich rice grains (0.04 mg kg−1). Five studied parent materials all had a significant effect on soil Se content but had little effect on Se bioavailability (p < 0.05). CEC, elevation, and SOM, as well as the soil contents of Cu, Zn, and Mn were positively correlated with soil Se content, but pH, MAP, and MAT were negatively correlated. Correspondingly, Se bioavailability was negatively correlated with SOM and soil Zn content, but positively correlated with MAP and grain contents of Cu, Zn, and Mn. Furthermore, partial least squares path analysis revealed the interactive impacts of the influencing factors on Se accumulation and bioavailability in soils. On this basis, prediction models were established to predict Se accumulation and bioavailability in paddy soils, thereby providing theoretical support for developing efficient control measures to meet Se challenges in agriculture.

The R-Process Alliance: Abundance Universality among Some Elements at and between the First and Second R-Process Peaks* * Based on archival observations made with the NASA/ESA Hubble Space Telescope (program GO-7348, program GO-8342, program GO-9455, program GO-14161, and program GO-14672) and observations collected from the Keck Observatory Archive (program U25H).

We present new observational benchmarks of rapid neutron-capture process (r-process) nucleosynthesis for elements at and between the first (A ∼ 80) and second (A ∼ 130) peaks. Our analysis is based on archival ultraviolet and optical spectroscopy of eight metal-poor stars with Se (Z = 34) or Te (Z = 52) detections, whose r-process enhancement varies by more than a factor of 30 (−0.22 ≤ [Eu/Fe] ≤ +1.32). We calculate ratios among the abundances of Se, Sr through Mo (38 ≤ Z ≤ 42), and Te. These benchmarks may offer a new empirical alternative to the predicted solar system r-process residual pattern. The Te abundances in these stars correlate more closely with the lighter r-process elements than the heavier ones, contradicting and superseding previous findings. The small star-to-star dispersion among the abundances of Se, Sr, Y, Zr, Nb, Mo, and Te (≤0.13 dex, or 26%) matches that observed among the abundances of the lanthanides and third r-process-peak elements. The concept of r-process universality that is recognized among the lanthanide and third-peak elements in r-process-enhanced stars may also apply to Se, Sr, Y, Zr, Nb, Mo, and Te, provided the overall abundances of the lighter r-process elements are scaled independently of the heavier ones. The abundance behavior of the elements Ru through Sn (44 ≤ Z ≤ 50) requires further study. Our results suggest that at least one relatively common source in the early Universe produced a consistent abundance pattern among some elements spanning the first and second r-process peaks.

Red snapper (Lutjanus campechanus) abundance on oil and gas platforms based on mark–recapture methods in the northern Gulf of Mexico

Oil and gas platforms provide reef habitat for many fish species on continental shelves. Red snapper ( Lutjanus campechanus) are an important component of these communities in the Gulf of Mexico, but abundance estimates are difficult to obtain. Hydroacoustic and visual-video surveys have been applied in previous abundance estimates, but such methods have difficulties. To improve abundance and fishing mortality ( F) estimates, mark–recapture methods were applied to red snapper at 22 platforms in the northern Gulf of Mexico from February 2017 through May 2020. Estimates were adjusted for emigration, tagging mortality, natural mortality, fisher nonreporting, and tag retention. Mean ± SE abundance·platform–1 (563 ± 107, range = 109–1407) and F (0.36, range = 0–1.25·platform–1) were not significantly affected by year, location, depth, or distance-from-shore. Based on an estimated 904 platforms, there were 508 952 (900 845 kg) red snapper on platforms. This indicated that red snapper on platforms accounted for only 1.2% of the 2016 Gulf of Mexico red snapper biomass. Thus, required removal of platforms will not significantly affect the red snapper stock in this area.

Geometallurgical ore characterization of the high-grade polymetallic unconformity-related uranium deposit

ABSTRACT Cigar Lake is a polymetallic, unconformity-related uranium deposit with complex geochemistry and mineralogy located in the eastern Athabasca Basin of northern Saskatchewan, Canada. Variable concentrations and spatial distributions of elements of concern, such as As, Mo, Ni, Co, Se, and Zr, associated with the high-grade tetravalent uranium ores [UO2+x; U(SiO4)1–x(OH)4x] present unique mining, metallurgical, and environmental challenges. Sulfide and arsenide minerals have significant control over As, Mo, Ni, Co, and Se abundances and have properties that affect element of concern mobility, thus requiring consideration during mineral processing, mine-effluent water treatment, and long-term tailings management. The U-bearing (uraninite, coffinite) and metallic arsenide (nickeline, often called “niccolite” in the past), sulfarsenide (gersdorffite, cobaltite), and sulfide (chalcopyrite, pyrite, galena, bornite, chalcocite, sphalerite, pyrrhotite) minerals provide the main controls on the distributions of the elements of concern. Arsenic, Ni, and Co occur primarily in a reduced state as 1:1 molar ratio, Ni-Co:As, arsenide, and sulfarsenide minerals such as gersdorffite, nickeline, and cobaltite. Molybdenum occurs within molybdenite and uraninite. Selenium occurs within coffinite, sulfide, and sulfarsenide minerals. Zirconium is found within detrital zircon and coffinite. The spatial distribution and paragenesis of U-, As-, and S-bearing minerals are a result of the elemental composition, pH, and redox conditions of early formational and later meteoric fluids that formed and have modified the deposit through access along lithostratigraphic permeability and tectonic structures. Using the holistic geometallurgical paradigm presented here, the geochemistry and mineral chemistry at Cigar Lake can be used to optimize and reduce risk during long-term mine and mill planning.

Reinjection flow field-flow fractionation method for nanoparticle quantitative analysis in unknown and complex samples

An analytical challenge that arises in environmental and food analysis is to quantify heterogeneous nanoparticles especially in polydisperse and complex samples. The method stated herein based on the reinjection asymmetrical flow field-flow fractionation (AF4 × AF4) coupled with inductively coupled plasma-mass spectrometer (ICP-MS) and statistical deconvolution allowed for identifying the molecular weight (Mw) and selenium abundance of the low Mw protein fractions (ca. < 132 kDa) in an unknown and complex sample (e.g., selenium-rich soybean protein isolates (Se-SPI)). A non-linear decay crossflow program was also developed to get better resolution and shorter elution time for both low and high Mw components. The concept of the reinjection method was based on the excellent ability for reducing sample complexity regarding the size fractionation, and peak reproducibility under the identical conditions of AF4 system. The standard protein mixture was used as a proof-of-principle sample. The results showed the underlying peaks predicted by the reinjection method were agreed with the separation result using the standard mixture (the relative standard deviation of peak locations < 1%), which indicated the reinjection method could provide an accurate assessment of the underlying peak number and location, and was promising to minimize the overfitting problem for statistic deconvolution. Interestingly, significant differences of Se abundance in protein fractions were observed in the low Mw range for Se-SPI, ranging from 0.28 to 1.66 cps/V with the Mw ranging from 13.75 kDa to 104.17 kDa, which indicated significant differences in the ability of binding Se for these selenium-rich proteins in Se-SPI.

Tissue localization of selenium of parental or dietary origin in rainbow trout (Oncorhynchus mykiss) fry using LA-ICP MS bioimaging

Abstract In relation to the decrease of selenium (Se) content in aquafeeds, the impact of level and form of parental and dietary Se supplementation was investigated in rainbow trout fry using laser ablation-inductively coupled plasma mass spectrometry (LA-ICP MS) bioimaging. The offspring of rainbow trout broodstock, fed either a control diet without any Se supplementation (0.3 mg Se/kg diet) or a diet supplemented with Se (0.6 mg Se/kg diet) either as sodium selenite or hydroxy-selenomethionine, were sampled at swim-up fry stage or after 11 weeks of cross-feeding. Total body Se levels were influenced by parental Se nutrition in swim-up fry and by direct Se feeding in 11-week fry with higher levels in the Se-supplemented groups compared with the control and the highest levels in the hydroxy-selenomethionine treatment. The Se retention was lower for dietary sodium selenite. Selenomethionine levels increased when Se was provided as hydroxy-selenomethionine. LA-ICP MS maps revealed yolk in swim-up fry and intestine, liver, and kidney in 11-week fed fry as tissues with high Se abundance. In swim-up fry, muscle Se was the highest abundant when parents were fed hydroxy-selenomethionine. In 11-week fed fry, muscle Se abundance was higher in the head part of fry fed both Se-supplemented diets, but only in the tail part of fry fed hydroxy-selenomethionine. Liver Se abundance was higher in fry fed sodium selenite compared with the control diet supporting the hypothesis that tissue Se distribution can be influenced by parental and dietary Se forms and levels.

Oral Supplementation With Bovine Colostrum Prevents Septic Shock and Brain Barrier Disruption During Bloodstream Infection in Preterm Newborn Pigs.

Preterm infants have increased risk of neonatal sepsis, potentially inducing brain injury, and they may benefit from early initiation of enteral milk feeding. Using preterm pigs as models, we hypothesized that early provision of bovine colostrum to parentally nourished newborns protects against sepsis and neuroinflammation during bloodstream infection. Preterm newborn pigs were administered 10 CFU/kg of intra-arterial Staphylococcus epidermidis (SE, an opportunistic pathogen often causing sepsis in preterm infants), followed by administration of total parenteral nutrition (TPN, SE + TPN, n = 15) or oral provision of bovine colostrum with supplementary parenteral nutrition (SE + COL, n = 14), and compared with uninfected, TPN-nourished controls (CON + TPN, n = 11). SE-infected animals showed multiple signs of sepsis, including lethargy, hypotension, respiratory acidosis, internal organ hemorrhages, cellular responses (leukopenia, thrombocytopenia), brain barrier disruption, and neuroinflammation. At 24 h, colostrum supplementation reduced the SE abundance in blood and cerebrospinal fluid (CSF, both P < 0.05). Furthermore, colostrum feeding normalized arterial blood pressure (38.5 ± 1.20 vs. 30.6 ± 3.79 mmHg), pH (7.37 ± 0.02 vs. 7.10 ± 0.07), and lactate (1.01 ± 0.11 vs. 4.20 ± 1.20 mM, all P < 0.05), and increased motor activity, to levels in controls (P < 0.001). Finally, colostrum-fed animals showed reduced blood-CSF barrier permeability and CSF leukocyte levels, and this was accompanied by normalized gene expression of tight junction proteins (Occludin, Claudin-5, both P < 0.05) and reduced expression of leukocyte chemoattractants (CXCL9-11, all P < 0.01). Early oral supplementation with bovine colostrum prevents septic shock and ameliorates brain barrier disruption and neuroinflammation during bloodstream infection in preterm pigs. Bovine colostrum supplementation may improve resistance against systemic infection in immature, immune-compromised preterm infants.

Neutron-capture Elements in Planetary Nebulae: First Detections of Near-infrared [Te iii] and [Br v] Emission Lines* †

Abstract We have identified two new near-infrared (NIR) emission lines in the spectra of planetary nebulae arising from heavy elements produced by neutron-capture reactions: [Te iii] 2.1019 μm and [Br v] 1.6429 μm. [Te iii] was detected in both NGC 7027 and IC 418, while [Br v] was seen in NGC 7027. The observations were obtained with the medium-resolution spectrograph Espectrógrafo Multiobjeto Infra-Rojo (EMIR) on the 10.4 m Gran Telescopio Canarias at La Palma, and with the high-resolution Immersion GRating INfrared Spectrometer (IGRINS) on the 2.7 m Harlan J. Smith telescope at McDonald Observatory. New calculations of atomic data for these ions, specifically A-values and collision strengths, are presented and used to derive ionic abundances of Te2+ and Br4+. We also derive ionic abundances of other neutron-capture elements detected in the NIR spectra, and estimate total elemental abundances of Se, Br, Kr, Rb, and Te after correcting for unobserved ions. Comparison of our derived enrichments to theoretical predictions from asymptotic giant branch (AGB) evolutionary models shows reasonable agreement for solar metallicity progenitor stars of ∼2–4 M ⊙. The spectrally isolated [Br v] 1.6429 μm line has advantages for determining nebular Br abundances over optical [Br iii] emission lines that can be blended with other features. Finally, measurements of Te are of special interest because this element lies beyond the first peak of the s-process, and thus provides new leverage on the abundance pattern of trans-iron species produced by AGB stars.

A method for Se isotope analysis of low ng-level geological samples via double spike and hydride generation MC-ICP-MS

The isotopic signature of the chalcophile, redox-sensitive and moderately volatile element Se in geological materials may offer valuable new insights into the origin and evolution of volatiles in planetary systems. Here, we report a new method for Se isotope determination of low Se containing samples relevant to the Earth's mantle reservoir. We present a method that combines a double spike and hydride generation sample introduction system with a ThermoFisher Scientific® NeptunePlus™ MC-ICP-MS. The measurement routine takes advantage of methane injection in the instrument source during measurement, resulting in enhanced Se signals and suppression of polyatomic interferences. Purification of Se from natural samples was simplified by employing conventional ion exchange chromatography procedures. An external reproducibility of 0.15‰ (2σ) on δ82/76Se values for measurements performed on natural samples with Se abundances down to ~5ng is obtained. We demonstrate that our technique allows the determination of Se isotope signatures of low Se-bearing geological materials with complex matrices such as mafic igneous rocks, which is essential to extend the Se isotopic investigation to Se-depleted planetary reservoirs such as the Earth's mantle.

Identification of Near-infrared [Se iii] and [Kr vi] Emission Lines in Planetary Nebulae∗

Abstract We identify [Se iii] 1.0994 μm in the planetary nebula (PN) NGC 5315 and [Kr vi] 1.2330 μm in three PNe from spectra obtained with the Folded-Port InfraRed Echellette (FIRE) spectrometer on the 6.5 m Baade Telescope. Se and Kr are the two most widely detected neutron-capture elements in astrophysical nebulae, and can be enriched by s-process nucleosynthesis in PN progenitor stars. The detection of [Se iii] 1.0994 μm is particularly valuable when paired with observations of [Se iv] 2.2864 μm, as it can be used to improve the accuracy of nebular Se abundance determinations, and allows Se ionization correction factor (ICF) schemes to be empirically tested for the first time. We present new effective collision strength calculations for Se2+ and Kr5+, which we use to compute ionic abundances. In NGC 5315, we find that the Se abundance computed from Se3+/H+ is lower than that determined with ICFs that incorporate Se2+/H+. We compute new Kr ICFs that take Kr5+/H+ into account, by fitting correlations found in grids of Cloudy models between Kr ionic fractions and those of more abundant elements, and use these to derive Kr abundances in four PNe. Observations of [Se iii] and [Kr vi] in a larger sample of PNe, with a range of excitation levels, are needed to rigorously test the ICF prescriptions for Se and our new Kr ICFs.

Origin of highly siderophile and chalcogen element fractionations in the components of unequilibrated H and LL chondrites

Osmium isotopic compositions, abundances of highly siderophile elements (HSE: platinum group elements, Re and Au), the chalcogen elements S, Se and Te and major and minor elements were analysed in physically separated size fractions and components of the ordinary chondrites WSG 95300 (H3.3, meteorite find) and Parnallee (LL3.6, meteorite fall). Fine grained magnetic fractions are 268-65 times enriched in HSE compared to the non-magnetic fractions. A significant deviation of some fractions of WSG 95300 from the 4.568 Ga 187Re-187Os isochron was caused by redistribution of Re due to weathering of metal. HSE abundance patterns show that at least four different types of HSE carriers are present in WSG 95300 and Parnallee. The HSE carriers display (i) CI chondritic HSE ratios, (ii) variable Re/Os ratios, (iii) lower than CI chondritic Pd/Ir and Au/Ir and (iv) higher Pt/Ir and Pt/Ru than in CI chondrites. These differences between components clearly indicate the loss of refractory HSE carrier phases before accretion of the components. Tellurium abundances correlate with Pd and are decoupled from S, suggesting that most Te partitioned into metal during the last high-temperature event. Tellurium is depleted in all fractions compared to CI chondrite normalized Se abundances. The depletion of Te is likely associated with the high temperature history of the metal precursors of H and LL chondrites and occurred independent of the metal loss event that depleted LL chondrites in siderophile elements. Most non-magnetic and slightly magnetic fractions have S/Se close to CI chondrites. In contrast, the decoupling of Te and Se from S in magnetic fractions suggests the influence of volatility and metal-silicate partitioning on the abundances of the chalcogen elements. The influence of terrestrial weathering on chalcogen element systematics of these meteorites appears to be negligible.

The isotope composition of selenium in chondrites constrains the depletion mechanism of volatile elements in solar system materials

Solar nebula processes led to a depletion of volatile elements in different chondrite groups when compared to the bulk chemical composition of the solar system deduced from the Sun's photosphere. For moderately-volatile elements, this depletion primarily correlates with the element condensation temperature and is possibly caused by incomplete condensation from a hot solar nebula, evaporative loss from the precursor dust, and/or inherited from the interstellar medium. Element concentrations and interelement ratios of volatile elements do not provide a clear picture about responsible mechanisms. Here, the abundance and stable isotope composition of the moderately- to highly-volatile element Se are investigated in carbonaceous, ordinary, and enstatite chondrites to constrain the mechanism responsible for the depletion of volatile elements in planetary bodies of the inner solar system and to define a δ82/78Se value for the bulk solar system. The δ82/78Se of the studied chondrite falls are identical within their measurement uncertainties with a mean of −0.20±0.26‰ (2 s.d., n=14, relative to NIST SRM 3149) despite Se abundance depletions of up to a factor of 2.5 with respect to the CI group. The absence of resolvable Se isotope fractionation rules out a kinetic Rayleigh-type incomplete condensation of Se from the hot solar nebula or partial kinetic evaporative loss on the precursor material and/or the parent bodies. The Se depletion, if acquired during partial condensation or evaporative loss, therefore must have occurred under near equilibrium conditions to prevent measurable isotope fractionation. Alternatively, the depletion and cooling of the nebula could have occurred simultaneously due to the continuous removal of gas and fine particles by the solar wind accompanied by the quantitative condensation of elements from the pre-depleted gas. In this scenario the condensation of elements does not require equilibrium conditions to avoid isotope fractionation. The results further suggest that the processes causing the high variability of Se concentrations and depletions in ordinary and enstatite chondrites did not involve any measurable isotope fractionation. Different degrees of element depletions and isotope fractionations of the moderately-volatile elements Zn, S, and Se in ordinary and enstatite chondrites indicate that their volatility is controlled by the thermal stabilities of their host phases and not by the condensation temperature under canonical nebular conditions.

The evolution of the global selenium cycle: Secular trends in Se isotopes and abundances

The Earth’s surface has undergone major transitions in its redox state over the past three billion years, which have affected the mobility and distribution of many elements. Here we use Se isotopic and abundance measurements of marine and non-marine mudrocks to reconstruct the evolution of the biogeochemical Se cycle from ∼3.2Gyr onwards. The six stable isotopes of Se are predominantly fractionated during redox reactions under suboxic conditions, which makes Se a potentially valuable new tool for identifying intermediate stages from an anoxic to a fully oxygenated world. δ82/78Se shows small fractionations of mostly less than 2‰ throughout Earth’s history and all are mass-dependent within error. In the Archean, especially after 2.7Gyr, we find an isotopic enrichment in marine (+0.37±0.27‰) relative to non-marine samples (−0.28±0.67‰), paired with increasing Se abundances. Student t-tests show that these trends are statistically significant. Although we cannot completely rule out the possibility of volcanic Se addition, these trends may indicate the onset of oxidative weathering on land, followed by non-quantitative reduction of Se oxyanions during fluvial transport. The Paleoproterozoic Great Oxidation Event (GOE) is not reflected in the marine δ82/78Se record. However, we find a major inflection in the secular δ82/78Se trend during the Neoproterozoic, from a Precambrian mean of +0.42±0.45‰ to a Phanerozoic mean of −0.19±0.59‰. This drop probably reflects the oxygenation of the deep ocean at this time, stabilizing Se oxyanions throughout the water column. Since then, reduction of Se oxyanions has likely been restricted to anoxic basins and diagenetic environments in sediments. In light of recent Cr isotope data, it is likely that oxidative weathering before the Neoproterozoic produced Se oxyanions in the intermediate redox state SeIV, whereas the fully oxidized species SeVI became more abundant after the Neoproterozoic rise of atmospheric oxygen.

Mineralogical control of selenium, tellurium and highly siderophile elements in the Earth’s mantle: Evidence from mineral separates of ultra-depleted mantle residues

The budget of Se–Te and other highly siderophile elements (HSEs) in major silicate and oxide mineral separates (olivine, orthopyroxene, clinopyroxene, spinel), and intergranular fine components of an ultra-refractory harzburgite have been determined via isotope dilution hydride generation ICPMS after mineral separation, high-pressure acid digestion and chemical purification. In addition, x-ray computed micro-tomography (micro-CT) has been performed in order to constrain and illustrate the original location, distribution and size of sulfides and/or alloys inside their intact, bulk harzburgite matrix. The results show that the whole-rock Se–Te budget of mantle residues, that are devoid of base metal sulfides (BMS) after high degrees of partial melting (F≈23%), is almost completely controlled by olivine-hosted micro-inclusions and intergranular fractions of platinum group minerals (PGMs). The scarcity and heterogeneous distribution of intergranular PGMs generally sized 3–5μm in the harzburgite are revealed by 3D micro-CT, while PGM inclusions in olivine are smaller than 2.5μm. The heterogeneous distribution of these microphases as well as the range of Se–Te contents in the bulk harzburgite complicate a quantification of individual contributions of separates to the whole-rock Se–Te budget. However, PGM micro-inclusions in olivine with residual-type CI chondrite-normalized HSE patterns and suprachondritic Se/Te ratios between 30 and 218 (Se/TeCI chondrite=9) host close to 100% of the bulk rock Se. Interstitial fine components up to 125μm grain size may contribute only minor amounts of Se, but up to 50% of Te to the bulk harzburgite and show subchondritic Se/Te ratios of ca. 4, resembling metasomatic PGM signatures. In dependence on increasing proportions of interstitial and metasomatic PGMs vs. olivine-hosted residual PGMs, the bulk rock Te contents may increase and the Se/Te ratios decrease. The systematics seen in mineral separates of one harzburgitic sample resembles the entire spectrum of Se–Te signatures of all suites of peridotites and host phases so far published. The results are consistent with a higher compatibility of Se in covalent monosulfides compared to Te that prefers sulfide melts. It is further consistent with the stabilization of residual PGMs after Mss exhaustion as well as with formation of metasomatic PGMs in a S-Cu-volatile-rich sulfide melt. Altogether this reconciles a higher incompatibility of Te over Se during partial mantle melting, subsequent removal of Te over Se with Cu-Ni-rich sulfide fractionation from high-degree partial mantle melts, and explains the similar Te but higher Se abundances in MORBs compared to peridotites that is globally observed.

NEW DETECTIONS OF ARSENIC, SELENIUM, AND OTHER HEAVY ELEMENTS IN TWO METAL-POOR STARS

We use the Space Telescope Imaging Spectrograph on board the Hubble Space Telescope to obtain new high-quality spectra covering the 1900 to 2360 Angstrom wavelength range for two metal-poor stars, HD 108317 and HD 128279. We derive abundances of Cu II, Zn II, As I, Se I, Mo II, and Cd II, which have not been detected previously in either star. Abundances derived for Ge I, Te I, Os II, and Pt I confirm those derived from lines at longer wavelengths. We also derive upper limits from the non-detection of W II, Hg II, Pb II, and Bi I. The mean [As/Fe] ratio derived from these two stars and five others in the literature is unchanged over the metallicity range -2.8 < [Fe/H] < -0.6, <[As/Fe]> = +0.28 +/- 0.14 (std. dev. = 0.36 dex). The mean [Se/Fe] ratio derived from these two stars and six others in the literature is also constant, <[Se/Fe]> = +0.16 +/- 0.09 (std. dev. = 0.26 dex). The As and Se abundances are enhanced relative to a simple extrapolation of the iron-peak abundances to higher masses, suggesting that this mass region (75 < A < 82) may be the point at which a different nucleosynthetic mechanism begins to dominate the quasi-equilibrium alpha-rich freezeout of the iron peak. <[CuII/CuI]> = +0.56 +/- 0.23 in HD 108317 and HD 128279, and we infer that lines of Cu I may not be formed in local thermodynamic equilibrium in these stars. The [Zn/Fe], [Mo/Fe], [Cd/Fe], and [Os/Fe] ratios are also derived from neutral and ionized species, and each ratio pair agrees within the mutual uncertainties, which range from 0.15 to 0.52 dex.

SELENIUM AND SULFUR CONCENTRATIONS IN COUNTRY ROCKS FROM THE DULUTH COMPLEX, MINNESOTA, USA: IMPLICATIONS FOR FORMATION OF THE Cu-Ni-PGE SULFIDES

Various studies suggest that the formation of a magmatic Ni-Cu-platinum group element (PGE) sulfide deposit requires addition of S from the country rocks into the magma. Many sulfide deposits have S/Se ratios higher than primary magmas, which is attributed to the preferential addition of S from the country rocks. However, this has not been clearly demonstrated because most studies do not determine Se in the country rocks, partly because, although Se concentration in igneous rocks can be assessed by most routine analytical techniques, their detection limits are too low for measuring with precision the level of Se in sedimentary rocks. We have determined Se abundances, using thiol cotton fiber (TCF) combined with instrumental neutron activation analysis (INAA), S, and delta (super 34) S on the magmatic sulfides of the Duluth Complex and on the host-rock sediments of the Virginia Formation. Our data show that the pelitic and metapelitic rocks of the Virginia Formation are characterized by low S/Se ratios ( approximately 3,000), close to the mantle values, whereas the S-rich layer known as the bedded pyrrhotite unit has high S/Se ratios ( approximately 20,000). Consequently, most of the Virginia Formation sediments and xenoliths are unsuitable as a source of S because they have S/Se ratios and delta (super 34) S values lower than those of the mineralized rocks (<10,000). Only the bedded pyrrhotite unit, which is present at the contact with the intrusion and as partly digested xenoliths within the intrusion, has S/Se ratios and delta (super 34) S values higher than those of the magmatic sulfides and could thus be the source of the S. Furthermore, the presence of sulfides in the norites around the xenoliths suggests that the S was released from the xenolith during melting of the xenolith. Detailed sampling from the xenoliths into the norite shows that the S/Se ratio and delta (super 34) S decrease with distance from the xenolith. Our results favor a mechanism of crustal S contamination by in situ assimilation of bedded pyrrhotite unit xenoliths.

Chalcophile and siderophile elements in sulphide inclusions in eclogitic diamonds and metal cycling in a Paleoproterozoic subduction zone

In the central Slave craton, eclogitic diamonds are suggested to have formed during Paleoproterozoic subduction in a meta-gabbroic substrate representing former lower oceanic crust that interacted with serpentinite-derived fluids at high fluid–rock ratios. In order to assess the behaviour of chalcophile and siderophile elements (CSE) during this process, we measured trace-element concentrations of sulphide inclusions in diamonds from the Diavik mine by laser ablation ICPMS. The nitrogen systematics of the diamonds (average N concentration of ∼600ppm and aggregation state 4% N as B-aggregates) indicate average mantle residence temperatures of ∼1050°C for a 1.85Ga formation age, corresponding ∼170km depth. Based on the available evidence from natural samples and experiments, we suggest that the highly siderophile elements (HSE: Os, Ir, Ru, Rh, Pd, Pt, Re) except Au behaved largely conservatively during fluid-induced metamorphism, which may point to a reducing and Cl-poor nature of the fluid. The abundances of the moderately siderophile and chalcophile elements Cr, Co, Ni, Cu, Ag, Sn, Mo and W may also have changed little, whereas As, Sb, Tl, Pb and Bi may have been mobilised from the subducting lower oceanic crust. The partitioning of CSE in eclogite and geochemical behaviour during oceanic crust formation was assessed for inferred conservative elements. Assuming an average sulphide mode of 0.3wt.% for the oceanic crust, its abundances of HSE, Cu, Mo, Se and Te can mostly be accounted for by sulphide minerals alone. Lithophile behaviour of W, Cd, In and Sn and enrichment in residual melts may explain their lower abundances in the gabbroic eclogitic sulphide inclusions compared to MORB sulphide. These elements, as well as Cr, Co, Ni, Zn and Ga require additional host phases both in eclogite, where rutile partitions significant amounts of Cr, Zn, W, Ga and Sn, and in the oceanic crust.

Atomic data for neutron-capture elements

We present multi-configuration Breit-Pauli AUTOSTRUCTURE calculations of distorted-wave photoionization (PI) cross sections, and total and partial final-state resolved radiative recombination (RR) and dielectronic recombination (DR) rate coefficients for the first six ions of the trans-iron element Se. These calculations were motivated by the recent detection of Se emission lines in a large number of planetary nebulae. Se is a potentially useful tracer of neutron-capture nucleosynthesis, but accurate determinations of its abundance in photoionized nebulae have been hindered by the lack of atomic data governing its ionization balance. Our calculations were carried out in intermediate coupling with semi-relativistic radial wavefunctions. PI and recombination data were determined for levels within the ground configuration of each ion, and experimental PI cross-section measurements were used to benchmark our results. For DR, we allowed dn=0 core excitations, which are important at photoionized plasma temperatures. DR is the dominant recombination process for each of these Se ions at temperatures representative of photoionized nebulae (~10^4 K). To estimate the uncertainties of these data, we compared results from three different configuration-interaction expansions for each ion, and tested the sensitivity of the results to the radial scaling factors in the structure calculations. We find that the internal uncertainties are typically 30-50% for the direct PI cross sections and ~10% for the computed RR rate coefficients, while those for low-temperature DR can be considerably larger (from 15-30% up to two orders of magnitude) due to the unknown energies of near-threshold autoionization resonances. The results are suitable for incorporation into photoionization codes used to numerically simulate astrophysical nebulae, and will enable robust determinations of nebular Se abundances.

The Abundances of Light Neutron‐Capture Elements in Planetary Nebulae. I. Photoionization Modeling and Ionization Corrections

We have conducted a large-scale survey of 120 planetary nebulae (PNe) to search for the near-infrared emission lines [Kr III] 2.199 μm and [Se IV] 2.287 μm. The neutron (n)-capture elements Se and Kr may be enriched in a PN if its progenitor star experienced s-process nucleosynthesis and third dredge-up. In order to determine Se and Kr abundances, we have added these elements to the atomic databases of the photoionization codes Cloudy and XSTAR, which we use to derive ionization correction factors (ICFs) to account for the abundances of unobserved Se and Kr ions. However, much of the atomic data governing the ionization balance of these two elements are unknown, and have been approximated from general principles. We find that uncertainties in the atomic data can lead to errors approaching 0.3 dex in the derived Se abundances and up to 0.2-0.25 dex for Kr. To reduce the uncertainties in the Kr ionization balance stemming from the approximate atomic data, we have modeled 10 bright PNe in our sample, selected because they exhibit emission lines from multiple Kr ions in their optical and near-infrared spectra. We have empirically adjusted the uncertain Kr atomic data until the observed line intensities of the various Kr ions are adequately reproduced by our models. Using the adjusted Kr atomic data, we have computed a grid of models over a wide range of physical parameters (central star temperature, nebular density, and ionization parameter) and derived formulae that can be used to compute Se and Kr ICFs. In the second paper of this series, we will apply these ICFs to our full sample of 120 PNe, which comprises the first large-scale survey of n-capture elements in PNe.

Siderophile-element anomalies in CK carbonaceous chondrites: Implications for parent-body aqueous alteration and terrestrial weathering of sulfides

CK chondrites constitute the most oxidized anhydrous carbonaceous chondrite group; most of the Fe occurs in magnetite and in FeO-rich mafic silicates. The two observed CK falls (Karoonda and Kobe), along with thirteen relatively unweathered CK finds, have unfractionated siderophile-element abundance patterns. In contrast, a sizable fraction of CK finds (9 of 24 investigated) shows fractionated siderophile abundance patterns including low abundances of Ni, Co, Se and Au; the most extreme depletions are in Ni (0.24 of normal CK) and Au (0.14 of normal CK). This depletion pattern has not been found in other chondrite groups. Out of the 74 CK chondrites listed in the Meteoritical Bulletin Database (2006; excluded considerably paired specimens; see http://tin.er.usgs.gov/meteor/metbull.php) we analyzed 24 and subclassified the CK chondrites in terms of their chemical composition and sulfide mineralogy: sL (siderophiles low; six samples) for large depletions in Ni, Co, Se and Au (>50% of sulfides lost); sM (siderophiles medium; two CKs) for moderately low Ni and Co abundances (sulfides are highly altered or partly lost); sH (siderophiles high; one specimen) for enrichments in Ni, Co, Se and Au; ‘normal’ for unfractionated samples (13 samples). The sole sH sample may have obtained additional sulfide from impact redistribution in the parent asteroid. We infer that these elements became incorporated into sulfides after asteroidal aqueous processes oxidized nebular metal; thermal metamorphism probably also played a role in their mineral siting. The siderophile losses in the sL and sM samples are mainly the result of oxidation of pentlandite, pyrite and violarite by terrestrial alteration followed by leaching of the resulting phases. Some Antarctic CK chondrites have lost most of their sulfides but retained Ni, Co, Se and Au, presumably as insoluble weathering products.