Abundances Of Cu Research Articles

Binding of Cu+ and Cu2+ with peptides: Peptides = oxytocin, Arg8‐vasopressin, bradykinin, angiotensin‐I, substance‐P, somatostatin, and neurotensin

The intrinsic binding ability of 7 natural peptides (oxytocin, arg8 -vasopressin, bradykinin, angiotensin-I, substance-P, somatostatin, and neurotensin) with copper in 2 different oxidation states (CuI/II ) derived from different Cu+/2+ precursor sources have been investigated for their charge-dependent binding characteristics. The peptide-CuI/II complexes, [M-(n-1)H+nCuI ] and [M-(2n-1)H+nCuII ], are prepared/generated by the reaction of peptides with CuI solution/Cu-target and CuSO4 solution and are analyzed by using matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry. The MALDI mass spectra of both [M-(n-1)H+nCuI ] and [M-(2n-1)H+nCuII ] complexes show no mass shift due to the loss of ─H atoms in the main chain ─NH of these peptides by Cu+ and Cu2+ deprotonation. The measured m/z value indicates the reduction of CuI/II oxidation state into Cu0 during MALDI processes. The number and relative abundance of Cu+ bound to the peptides are greater compared with the Cu2+ bound peptides. Oxytocin, arg8 -vasopressin, bradykinin, substance-P, and somatostatin show the binding of 5Cu+ , and angiotensin-I and neurotensin show the binding of 7Cu+ from both CuI and Cu targets, while bradykinin shows the binding of 2Cu2+ , oxytocin, arg8 -vasopressin, angiotensin-I, and substance-P; somatostatin shows the binding of 3Cu2+ ; and neurotensin shows 4Cu2+ binding. The binding of more Cu+ with these small peptides signifies that the bonding characteristics of both Cu+ and Cu2+ are different. The amino acid residues responsible for the binding of both Cu+ and Cu2+ in these peptides have been identified based on the density functional theory computed binding energy values of Cu+ and the fragment transformation method predicted binding preference of Cu2+ for individual amino acids.

Elemental distribution in developing rice grains and the effect of flag-leaf arsenate exposure

We measured the bulk grain concentrations of arsenic (As), along with rubidium (Rb) and strontium (Sr) as indicators of phloem and xylem transport respectively, in rice (Oryza sativa cv. Italica Carolina) pulsed with arsenate (As(V)) at two exposure concentrations for 5 day periods at progressively later stages of grain fill, between anthesis and maturity, via the cut flag leaf. We compared these to unexposed (negative) controls and positive controls (pulsed with dimethylarsinic acid (DMA)), the most efficiency transported As species in rice. We collected elemental maps of As and micronutrient elements (Fe, Zn, Mn, Cu and Ni) from developing grains. Exposures were 25 or 100 μg/ml As(V). We used the spatial distribution of arsenic in the grain to infer the presence of As transporters. By exposing grains via the flag leaf rather than the roots, we were able to measure arsenic transport into the grain during filling under controlled conditions. Exposure to 100 μg/ml As(V) resulted in widespread As localization in both embryo and endosperm, especially in grains exposed to As at later stages of panicle development. This suggests loss of selective transport, likely to be the result of As toxicity. At 25 μg/ml As(V), As colocalized with Mn in the ovular vascular trace (OVT). Exposure to either As(V) or DMA reduced grain Fe, an effect more pronounced when exposure occurred earlier in grain development. The abundance of Cu and Zn were also reduced by As. Arsenic exposure later in grain development caused higher grain As concentrations, indicating the existence of As transporters whose efficiency increases during grain fill. We conclude that localization of As in the grain is a product of both As species and exposure concentration, and that high As(V) translocation from the flag leaf can result in high As concentrations in the endosperm.

Mineral Systems, Their Types, and Distribution in Nature: 2. Products of Contemporary Fumarole Activity at Tolbachik Volcano (Russia) and Vulcano (Italy)

The number of mineral species in which a certain chemical element is species-defining (according to statistical data up to 2015) has been specified. Seventy chemical elements are species-defining for 5044 minerals. The following chemical elements lead in the composition of minerals (number of mineral species in parentheses): oxygen (4115), hydrogen (2800), silicon (1471), calcium (1167), sulfur (1056), aluminium (985), sodium (949), iron (945), copper (636), phosphorus (597), arsenic (594), and magnesium (571). The distribution of mineral species by various systems in the products of contemporary fumarole activity at two volcanoes, Tolbachik in Kamchatka, Russia, and Vulcano in Sicily, Italy, has been compared. These locations were also compared for the distribution of species-defining elements. Thus, it has been determined that in fumaroles of both volcanoes, Tl, S, Cl, F and Na are “excessive,” present in minerals in elevated amounts, whereas H, Ca, Fe, and Mn are “deficient.” The abundance of Cu, Se, V, Mg, Zn, As, and F in minerals at Tolbachik is higher than the global mean values of these elements in the Earth’s crust, whereas the abundance is significantly lower at Vulcano. Sn, I, Br, K, Pb, Al, Fe, and Bi demonstrate the opposite behavior. Comparison of the Yadovitaya and Arsenatnaya fumaroles at the Tolbachik volcano showed that the products of the former are richer in H, Cl, Cu, S, K, O, Al, Fe, and Pb, and poorer in As, Ca, Mg, and Na as species-defining elements. In addition, V-and Mo-bearing minerals are found only at Yadovitaya, whereas minerals containing F, Ti, В, Те, and Zn are known only at Arsenatnaya.

Chemical abundances of 1111 FGK stars from the HARPS GTO planet search program

To understand the formation and evolution of the different stellar populations within our Galaxy it is essential to combine detailed kinematical and chemical information for large samples of stars. We derive chemical abundances of Cu, Zn, Sr, Y, Zr, Ba, Ce, Nd and Eu for a large sample of more than 1000 FGK dwarf stars with high-resolution ($R \sim$\,115000) and high-quality spectra from the HARPS-GTO program. The abundances are derived by a standard Local Thermodinamyc Equilibrium (LTE) analysis using measured Equivalent Widths (EWs) injected to the code MOOG and a grid of Kurucz ATLAS9 atmospheres. We find that thick disk stars are chemically disjunct for Zn and Eu and also show on average higher Zr but lower Ba and Y when compared to the thin disk stars. We also discovered that the previously identified high-$\alpha$ metal-rich population is also enhanced in Cu, Zn, Nd and Eu with respect to the thin disk but presents Ba and Y abundances lower on average, following the trend of thick disk stars towards higher metallities and further supporting the different chemical composition of this population. The ratio of heavy-s to light-s elements of thin disk stars presents the expected behaviour (increasing towards lower metallicities) and can be explained by a major contribution of low-mass AGB stars for s-process production at disk metallicities. However, the opposite trend found for thick disk stars suggests that intermediate-mass AGB stars played an important role in the enrichment of the gas from where these stars formed. Previous works in the literature also point to a possible primary production of light-s elements at low metallicities to explain this trend. Finally, we also find an enhancement of light-s elements in the thin disk at super solar metallicities which could be caused by the contribution of metal-rich AGB stars. (short version)

Geology, mineralization and sulfur isotopes geochemistry of the Mari Cu (Ag) Manto-type deposit, northern Zanjan, Iran

The Eocene volcano-sedimentary sequence, northern Zanjan, consist of 1.5km of shallow-marine sediments. These include sandstone, lapilli tuff, andesite, basalt and felsic volcanic rocks. The Mari deposit is strata-bound that hosted by the Eocene andesite rocks. The major copper sulfides are bornite, chalcocite, and chalcopyrite associated mainly with pyrite that show open-space filling, disseminated, vein-veinlet, and replacement textures. The abundances of Cu and Ag in the ore-bearing andesite are up to 40,000 and 70ppm respectively. Wall rock alterations include carbonatization, chloritization, epidotization, and sericitization. Sulfur isotope compositions have a negative range from δ34S=−2.7 to −3.4‰, suggesting the presence of a reducing environment resulting from activation of sulfate reducing bacteria. Mineralization formed two stages: stage one include volcanic activity and eruption of andesitic lava, in this stage syngenetic disseminated pyrites formed. In the second stage, increasing of the thickness of sediments, basin subsidence, and burial diagenesis accompanied with the entry of metal-rich fluids into the reduced host rock, caused the replacement of the first stage pyrites by copper sulfides. The geology, ore mineralogy, alteration characteristics and sulfur isotopic compositions suggest the Mari deposit may be classified as a Manto-type deposit.

Low Temperature Grown Graphene on Ultra-Long Copper Nanowire By Carbon-Enclosed Chemical Vapor Deposition As Stable Transparent Conducting Electrodes in Harsh Environments

Replacement of indium doped tin oxide (ITO) by metallic nanowires, metal mesh, CNT and graphene plays key role due to scarcity of indium and its brittleness for flexible optoelectronic devices. Copper nanowires synthesized by solution process are an attractive alternative to ITO due to the abundance of Cu and the low cost of solution process. However, it suffers oxidation and corrosion problems, which mainly affect the optoelectronic properties. Here, we proposed a new technique to achieve low temperature deposition of graphene to protect copper nanowire by carbon-enclosed chemical vapor deposition (CE-CVD) at 400 °C with a the low sheet resistance of 9 Ohms/sq and a transmittance of 85%. Graphene coted copper nanowire on glass show excellent oxidation resistance without sacrificing electrical conductivity even annealing at 240 °C in oxygen ambient more than 2 hr and also shows an excellent anti-corrosion in highly corrosive environments such as sea water, acidic and basic solutions. The highly stable non-corrosive and anti-oxidant graphene coated copper nanowire can be used as an alternative transparent conducting electrode (TCE) for emerging optoelectronic devices and applications working in harsh environments.

Cu–Ag sulfides as indicators of pre-porphyritic epithermal Au–Ag deposits in Northeastern Russia

Au–Ag mineralization of the Olcha and Teploe epithermal deposits underwent thermal metamorphism due to porphyritic intrusions. The presence of Bi-bearing galena and matildite in the ores (Teploe), Cu–Te-bearing naumannite (Olcha), the occurrence of middle- and high-temperature facies of metasomatic rocks (epidote and actinolite), and temperature formation conditions are related, firstly, to the influence of granitoids on the ore process, which supplied not only Cu and Mo, but also Bi, Te, and, secondly, to the heating of host rocks containing pre-porphyritic epithermal Au–Ag mineralization. The abundance of Cu–Ag sulfides and Cu-acanthite resulted from the enrichment of later mineral phases in Cu and Ag under the substance redistribution with the formation of Ag-acanthite ores. The data considered in the paper are of practical importance for regional forecasting of metallogenic constructions, exploration, and evaluation of the epithermal Au–Ag deposits.

Copper nanowire networks with transparent oxide shells that prevent oxidation without reducing transmittance.

Transparent conducting films of solution-synthesized copper nanowires are an attractive alternative to indium tin oxide due to the relative abundance of Cu and the low cost of solution-phase nanowire coating processes. However, there has to date been no way to protect Cu nanowires with a solution-phase process that does not adversely affect the optoelectric performance of Cu nanowire films. This article reports that the electrodeposition of zinc, tin, or indium shells onto Cu nanowires, followed by oxidation of these shells, enables the protection of Cu nanowire films against oxidation without decreasing film performance.

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.

Paragenesis of cobalt and nickel in the Black Butte shale-hosted copper deposit, Belt Basin, Montana, USA

The Black Butte copper deposits (formerly known as Sheep Creek) are a group of sediment hosted, laterally extensive Cu–(Co–Ag) deposits hosted in dolomitic shale of the mid-Proterozoic Newland Formation. Copper–cobalt mineralization occurs in zones of massive, laminated pyrite that were locally reworked and infiltrated by Cu-rich fluids during early diagenesis. Cobalt, along with substantial nickel and arsenic, mainly occurs as impurities within early, porous pyrite, or as minute grains of sulpharsenides (i.e., cobaltite, glaucodot, and/or alloclasite). Later thermal events remobilized the Co, Ni, and As to form intergrowths of siegenite (Co,Ni)3S4 and tennantite. The temperature of this later event is constrained by the mineralogical assemblage to have been relatively low, between 125 and 225 °C. Although many of the characteristics of SEDEX-type deposits are present at Black Butte (e.g., laterally extensive massive pyrite horizons, interbedded black shales, abundant barite and local phosphate horizons, and rifted continental margin setting), the lack of economic Pb and Zn mineralization in the main deposits, and the abundance of Cu with high Co, is more typical of sediment-hosted stratiform copper deposits. The Neihart Formation, a hematitic quartz sandstone resting below the base of the Belt Supergroup, may have been an important source bed for Cu–Co–Ni–Ag fluids. It is speculated that these fluids, ideal for forming Cu deposits, were expelled along growth faults near the margin of the Belt Basin and deposited metals on or just below the sea floor in a setting that is typical of SEDEX deposits. This unique mineral deposit model may have applications to other districts where Cu–Co-rich sulfides are deposited in an exhalative setting.

Petrography and geochemistry of the Shilu Fe–Co–Cu ore district, South China: Implications for the origin of a Neoproterozoic BIF system

The Shilu Fe–Co–Cu ore district is situated in the western Hainan Province of south China. This district consists of the upper Fe-rich layers and the lower Co–Cu ores, which are mainly hosted within the Neoproterozoic Shilu Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Three facies of metamorphosed BIFs, the oxide, the silicate–oxide and the sulfide–carbonate–silicate, have been identified within the Shilu Group. The oxide banded iron formation (BIF) facies (quartz itabirites or Fe-rich ores) consists of alternating hematite-rich and quartz-rich microbands. The silicate–oxide BIF facies (amphibolitic itabirites or Fe-poor ores) comprises alternating millimeter to tens of meter scale, magnetite–hematite-rich bands with calc-silicate-rich macro- to microbands. The sulfide–carbonate–silicate BIF facies (Co–Cu ores) contain alternating cobaltiferous pyrite, cobaltiferous pyrrhotite and chalcopyrite macrobands to microbands mainly with dolomite–calcite, but also with minor sericite–quartz bands. Blasto-oolitic, pelletoidal, colloidal, psammitic, and cryptocrystalline to microcrystalline textures, and blasto-bedding structures, which likely represent primary sedimentation, are often observed in the Shilu BIF facies.The Shilu BIFs and interbedded host rocks are generally characterized by relatively low but variable ∑REE concentrations, LREE depletion and/or MREE enrichment relative to HREE, and no Ce, Gd and Eu anomalies to strongly positive Ce, Gd and Eu anomalies in the upward-convex PAAS-normalized REY patterns, except for both the banded or impure dolostones with nil Ce anomaly to negative Ce anomalies and negative La anomalies, and the minor sulfide–carbonate–silicate BIF facies with moderately negative Eu anomalies. They also contain relatively low but variable HFSE abundances as Zr, Nb, Hf, Th and Ti, and relatively high but variable abundances of Cu, Co, Ni, Pb, As, Mn and Ba. The consistently negative εNd(t) values range from −4.8 to −8.5, with a TDM age of ca. 2.0Ga. In line with the covariations between Al2O3 and TiO2, Fe2O3+FeO and SiO2, Mn and Fe, Zr and Y/Ho and REE, and Sc and LREE, the geochemical and Sm–Nd isotopic features suggest that the precursors to the Shilu BIFs formed from a source dominated by seafloor-derived, high- to low temperature, acidic and reducing hydrothermal fluids but with variable input of detrital components in a seawater environment. Moreover, the involved detrital materials were sourced dominantly from an unknown, Paleoproterozoic or older crust, with lesser involvement from the Paleo- to Mesoproterozoic Baoban Group underlying the Shilu Group.The Shilu BIFs of various facies are interpreted to have formed in a shallow marine, restricted or sheltered basin near the rifted continental margin most likely associated with the break-up of Rodinia as the result of mantle superplume activity in South China. The seafloor-derived, periodically upwelling metalliferous hydrothermal plume/vent fluids under anoxic but sulfidic to anoxic but Fe2+-rich conditions were removed from the plume/vent and accumulated in the basin, and then variably mixed with terrigenous detrital components, which finally led to rhythmic deposition of the Shilu BIFs.

Metamorphic history of skarns, origin of their protolith and implications for genetic interpretation; an example from three units of the Bohemian Massif

*Corresponding author Skarns in the Svratka Unit, in the neighbouring part of the Moldanubian Zone and in the Kutna Hora Complex were studied with respect to their metamorphic evolution, major- and trace-element geochemistry, oxygen isotopic composition and zircon ages. Skarns form competent lenses and layers in metamorphosed siliciclastic rocks and preserve some early deformation structures and several equilibrium assemblages representing the products of successive metamorphic reactions. The main rock-forming minerals, garnet and clinopyroxene, are accompanied by less abundant magnetite, amphibole, plagioclase, epidote ± quartz. In the Svratka Unit the early prograde M 1 , prograde/peak M 2 , and retrograde M 3 metamorphic stages have been distinguished. Metamorphic conditions in skarns of the Moldanubian Zone are limited to a relatively narrow interval of amphibolite facies. The prograde and retrograde events in the Kutna Hora Complex skarns probably took place under amphibolite-facies conditions. The presence of magnetite and the increasing proportion of the andradite component in the garnet indicate locally increased oxygen fugacity. Skarn geochemistry does not show systematic differences in the skarn composition among the three units. The regional variations are exceeded by differences among samples from individual localities. The Al 2 O 3 /TiO 2 , Al 2 O 3 /Zr, TiO 2 /Nb ratios point to the variable proportion of the detrital material, combined in skarn protoliths with CaO and FeO, the major non-detrital components. The skarns exhibit elevated abundances of Cu, Zn, Sn and As. The Eu/Eu* ratio varies in the range of 0.5–8.6, the total REE contents vary from 8 to 345 ppm. The lowest ΣREE values (< 100 ppm) occur in skarns with magnetite mineralization. The wide intervals of ΣREE and Eu/Eu* values are interpreted to indicate variations in the temperature and redox conditions among layers of the same locality and at various localities. The oxygen isotope compositions of garnets, pyroxenes and amphiboles from skarns of the Svratka Unit exhibit a range of δ 18 O = 0.1 to 4.1 ‰. In situ (laser-ablation ICP-MS) U-Pb dating of zircon from one of the Svratka Unit skarn bodies yielded a wide range of ages (0.5–2.6 Ga), supporting the detrital origin of this zircon population. The skarn protoliths were probably rocks of mixed detrital-exhalative origin deposited on the sea floor . The geological position of skarns, with their structural and metamorphic record, probably reflect tectono-metamorphic evolution shared with that of their host rocks. The geochemical characteristics, including oxygen isotopic compositions and the presence of detrital zircons with a wide range of ages exclude metasomatic, and point to a sedimentary-exhalative mode of origin for the studied skarns.

Copper exchanged ultrastable zeolite Y – A catalyst for NH3-SCR of NOx from stationary biogas engines

NOx emissions will need to be controlled from gas engines, which in the future could be using a syngas/producer gas as a fuel (generated from the gasification of biomass). In anticipation of this need, the activity of a copper-exchanged ultrastabilized zeolite Y was investigated, for the selective catalytic reduction of NOx. The catalyst performance and properties were compared with reference samples of Cu-exchanged un-stabilized Y and Cu exchanged ZSM-5 zeolites. Activity was related to the number and nature of active centers, which were determined by in situ FTIR and TPD experiments using CO, NO, and NH3 as probe molecules. In the test reaction the ultrastabilized Cu-USY catalyst showed high activity at low temperatures and offered high hydrothermal resistance, whilst the Cu-ZSM-5 catalyst demonstrated the highest overall activity. The observed low temperature activity of the ultrastabilized Cu-USY catalyst was linked to the high abundance of Cu+ sites, which were detected by in situ FTIR analyses using CO adsorption.

Size distributions and sources of elements in particulate matter at curbside, urban and rural sites in Beijing

Abstract Size distributions of 29 elements in aerosols collected at urban, rural and curbside sites in Beijing were studied. High levels of Mn, Ni, As, Cd and Pb indicate the pollution of toxic heavy metals cannot be neglected in Beijing. Principal component analysis (PCA) indicates 4 sources of combustion emission, crust related sources, traffic related sources and volatile species from coal combustion. The elements can be roughly divided into 3 groups by size distribution and enrichment factors method (EFs). Group 1 elements are crust related and mainly found within coarse mode including Al, Mg, Ca, Sc, Ti, Fe, Sr, Zr and Ba; Group 2 elements are fossil fuel related and mostly concentrated in accumulation mode including S, As, Se, Ag, Cd, Tl and Pb; Group 3 elements are multi-source related and show multi-mode distribution including Be, Na, K, Cr, Mn, Co, Ni, Cu, Zn, Ga, Mo, Sn and Sb. The EFs of Be, S, Cr, Co, Ni, Cu, Ga, Se, Mo, Ag, Cd, Sb, Tl and Pb show higher values in winter than in summer indicating sources of coal combustion for heating in winter. The abundance of Cu and Sb in coarse mode is about 2-6 times higher at curbside site than at urban site indicating their traffic sources. Coal burning may be the major source of Pb in Beijing since the phase out of leaded gasoline, as the EFs of Pb are comparable at both urban and curbside sites, and about two times higher in winter than that in summer.

Route Toward High-Efficiency Single-Phase Cu$_{\bf 2}$ZnSn(S,Se)$_{\bf 4}$ Thin-Film Solar Cells: Model Experiments and Literature Review

Thin-film chalcogenide kesterites Cu <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ZnSnS <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> and Cu <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ZnSnSe <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">4</sub> (CZTSSe) are promising candidates for the next-generation thin-film solar cells. They exhibit a high natural abundance of Cu, Zn, Sn and S <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> , a high absorption coefficient, and a tunable direct bandgap between 1.0 and 1.5 eV. A prerequisite for the use of CZTSSe as absorber layers in photovoltaic applications on large scales is a detailed knowledge of the formation reaction. Recently, we have shown that a decomposition/formation equilibrium governs the formation reaction. The presence of Sn(S,Se) during the high-temperature preparation steps is essential to prevent decomposition. This improves the solar cell efficiency from 0.02% to 6.1%. In this paper, we show that the decomposition is universal. Absorbers produced by high-temperature coevaporation and samples produced by low-temperature precursor fabrication followed by annealing in a tube furnace in S or Se atmosphere are compared in order to elucidate that in all cases, the loss of Sn(S,Se) forms a degraded surface region. We demonstrate that the degraded surface of CZTSe absorbers contains grains of ZnSe. These new insights can be used to explain why some of the synthesis routines described in the literature yield much better efficiencies than others.

Rhenium–osmium isotope and platinum-group elements in the Xinjie layered intrusion, SW China: Implications for source mantle composition, mantle evolution, PGE fractionation and mineralization

The Xinjie mafic–ultramafic layered intrusion in the Emeishan large igneous province (ELIP) hosts Cu–Ni–platinum group element (PGE) sulfide ore layers within the lower part and Fe–Ti–V oxide-bearing horizons within the middle part. The major magmatic Cu–Ni–PGE sulfide ores and spatially associated cumulate rocks are examined for their PGE contents and Re–Os isotopic systematics. The samples yielded a Re–Os isochron with an age of 262 ± 27 Ma and an initial 187Os/ 188Os of 0.12460 ± 0.00011 ( γ Os( t) = −0.5 ± 0.1). The age is in good agreement with the previously reported U–Pb zircon age, indicating that the Re–Os system remained closed for most samples since the intrusion emplacement. They have near-chondritic γ Os( t) values ranging from −0.7 to −0.2, similar to those of the Lijiang picrites and Song Da komatiites. Exceptionally, two samples from the roof zone and one from upper sequence exhibit radiogenic γ Os( t) values (+0.6 to +8.6), showing minor contamination by the overlying Emeishan basalts. The PGE-rich ores contain relatively high PGE and small amounts of sulfides (generally less than 2%) and the abundance of Cu and PGE correlate well with S, implying that the distribution of these elements is controlled by the segregation and accumulation of a sulfide liquid. Some ore samples are poor in S (mostly <800 ppm), which may due to late-stage S loss caused by the dissolution of FeS from pre-existing sulfides through their interaction with sulfide-unsaturated flowing magma. The combined study shows that the Xinjie intrusion may be derived from ferropicritic magmas. The sharp reversals in Mg#, Cr/FeO T and Cr/TiO 2 ratios immediately below Units 2–4, together with high Cu/Zr ratios decreasing from each PGE ore layer within these cyclic units, are consistent with multiple magma replenishment episodes. The sulfides in the cumulate rocks show little evidence of PGE depletion with height and thus appear to have segregated from successive inputs of fertile magma. This suggests that the Xinjie intrusion crystallized from in an open magma system, e.g., a magma conduit. The compositions of the disseminated sulfides in most samples can be modeled by applying an R factor (silicate–sulfide mass ratio) of between 1000 and 8000, indicating the segregation of only small amounts of sulfide liquid in the parental ferropicritic magmas. Thus, continuous mixing between primitive ferropicritic magma and differentiated resident magma could lead to crystallization of chromite, Cr-bearing magnetite and subsequently abundant Fe–Ti oxides, thereby the segregation of PGE-rich Cu-sulfide. When considered in the light of previous studies on plume-derived komatiites and picrites worldwide, the close-to-chondritic Os isotopic composition for most Xinjie samples, Lijiang picrites and Song Da komatiites suggest that the ferropicritic magma in the ELIP were generated from a plume. This comprised recycled Neoproterozic oceanic lithosphere, including depleted peridotite mantle embedded with geochemically enriched domains. The ascending magmas thereafter interacted with minor (possibly <10%) subducted/altered oceanic crust. This comparison suggests that the komatiitic melts in the ELIP originated from a greater-than normal degree of melting of incompatible trace element depleted, refractory mantle components in the plume source.

Use of human bronchial epithelial cells (BEAS-2B) to study immunological markers resulting from exposure to PM 2.5 organic extract from Puerto Rico

Fine particulate air pollutants, mainly their organic fraction, have been demonstrated to be associated with cardiovascular and respiratory health problems. Puerto Rico has been reported to have the highest prevalence of pulmonary diseases (e.g., asthma) in the United States. The aim of this study was to assess, for the first time, the immunological response of human bronchial epithelial cells (BEAS-2B) to organic extracts isolated from airborne particulate matter (PM 2.5) in Puerto Rico. Organic extracts from PM 2.5 collected throughout an 8-month period (2000–2001) were pooled (composite) in order to perform chemical analysis and biological activity testing. BEAS-2B cells were exposed to PM 2.5 organic extract to assess cytotoxicity, levels of cytokines and relative gene expression of MHC-II, hPXR and CYP3A5. Our findings show that organic PM 2.5 consist of toxic as well as bioactive components that can regulate the secretion of cytokines in BEAS-2B, which could modulate inflammatory response in the lung. Trace element analyses confirmed the presence of metals in organic extracts highlighting the relative high abundance of Cu and Zn in polar organic extracts. Polar organic extracts exhibited dose-dependant toxicity and were found to significantly induce the release of interleukin 6 (IL-6), IL-1β and IL-7 while significantly inhibiting the secretion of IL-8, G-CSF and MCP-1. Moreover, MHC-II transcriptional activity was up-regulated after 24 h of exposure, whereas PXR and CYP3A5 were down-regulated. This research provides a new insight into the effects of PM 2.5 organic fractions on specific effectors and their possible role in the development of respiratory inflammatory diseases in Puerto Rico.

Peat records of human impacts on the atmosphere in Northwest China during the late Neolithic and Bronze Ages

Man has played a major role in shaping the landscape in inland China during the second half of the Holocene. However, little is known about the impact on atmospheric environments. Here we present a high-resolution peat record of atmospheric variations in Northwest China, which covers the late Neolithic and Bronze Ages. Ten heavy metallic elements (Pb, Zn, Fe, Mn, Cu, Co, Ni, Ti, V, and Al) were analyzed, and the abundances of Cu, Pb, and Zn were found to be significantly above their background levels during some periods while intensified human activities occurred in the adjacent Gansu–Qinghai area. Modern meteorological observations and sedimentological analyses indicate that the element-bearing aerosol was transported by the strengthened northeast wind. Four elements (Ti, V, Co, and Ni) exhibit coherent variations with Pb prior to 5500 cal a B.P., and thus they were used to reconstruct the background level of Pb. The human-induced Pb signal correlates well with the population inferred from archaeological excavations in the Liuwan Tombs in Qinghai Province, suggesting that human activities may have a great impact on the atmospheric environment in this area.

Isotopic and elemental abundances of copper and zinc in lunar samples, Zagami, Pele’s hairs, and a terrestrial basalt

We used ICP–MS to measure the elemental concentrations and isotopic abundances of Cu and Zn in: nine Ti-rich lunar basalts (10017, 10022, 10024, 10057, 70215, 71055, 74255, 75055, and 75075); size-separated samples prepared by sieving of pyroclastic black glass 74001, orange glass 74022, and the lunar soils 15021, 15231, 70181, and 79221; a basalt from the Piton des Neiges volcano, Reunion Island; two samples of Pele’s hairs from the Nyiragongo volcano, Democratic Republic of Congo, and the martian meteorite Zagami. The isotopic fractionation of zinc in lunar basalts and Zagami is mass dependent relative to a terrestrial standard (JMC 400882B). These and published results imply that lunar, terrestrial, meteoritic, and perhaps martian zinc all come from one or more reservoirs linked by mass-dependent fractionation processes. Relative to terrestrial basalts, Ti-rich lunar basalts are enriched in the heavier isotopes of Cu and Zn: we find for Ti-rich lunar basalts the following ranges and averages ±1 − σ (‰): δ 65Cu/ 63Cu ≡ δ 65Cu, 0.1–1.4, 0.5 ± 0.1‰ ( N = 7); δ 66Zn/ 64Zn ≡ δ 66Zn = 0.2–1.9, 1.2 ± 0.2‰ ( N = 8; 10017 excluded). For two terrestrial samples, we find δ 66Zn ∼ +0.3‰ and δ 65Cu ∼ 0‰, which are consistent with published values. The differences between the lunar basalts and terrestrial basalts could reflect minor, planetary-scale vaporization or igneous processes on the Moon. Data for size separates of the pyroclastic glasses 74001 and 74220 confirm the well-known surface correlation of Cu and Zn, but modeling calculations reveal no sharp differences between either the elemental ratios or the isotopic composition of grain interiors and exteriors. The absence of such differences indicates that the isotopic compositions for bulk samples are dominated by a light-isotope-rich surface component. Data for size separates of lunar soils also confirm the surface correlation of Cu and Zn, but an enrichment of heavy rather than light isotopes. Averages for bulk lunar soils from this work and the literature are (‰): δ 65Cu, from 1.4 to 4.1, average 3.0 ± 0.3 ( N = 9); δ 66Zn, from 2.2 to 6.4, average 4.0 ± 0.3 ( N = 14). As with the glasses, in all but soil 15231 our data show no strong differences between the isotopic composition of soil sub-samples with small and large grains. The size of the isotopic fractionation inferred for the surface component in the soils is 3× smaller than predicted by a published model of sputtering primarily by solar particles. At the same time, the observed fractionation is larger than predicted by calculations based on a model of micrometeorite impact heating and hydrodynamic quenching. Because impact heating appears unable to explain the observations, we conclude that sputtering must be important even though samples with very large isotopic fractionation of Cu and Zn have not yet been found.

Metals in quartz-hosted melt inclusions: Natural facts and experimental artifacts

Studies of melt inclusions trapped in magmatic phenocrysts can provide a new perspective on several key outstanding problems in the understanding of the genesis of orthomagmatic ore deposits, particularly with respect to the concentration of metals in parental magmas. The published data shows a mismatch between low and high abundances of Cu (and Ag) in unheated and remelted melt inclusions, respectively. This experimental study investigates the possibility that quartz-hosted rhyolitic melt inclusions may change their composition during laboratory heating under different conditions. Exceptional volatility of Cu and Ag and inert behavior of other metals (Zn, Pb, Mo, Sn, W) and lithophile trace elements at high temperature (850 °C) is demonstrated. Heating experiments with melt inclusions require specific conditions that should take the high volatility of Cu and Ag into account. The open system behavior of Cu and Ag can also affect the composition of melt inclusions within the time frame between trapping and eruption