Copper Isotopic Analysis in Geological and Biological Reference Materials by MC‐ICP‐MS

The characterisation of relative copper isotope amount ratios (δ⁶⁵Cu) helps constrain a variety of geochemical processes occurring in the geosphere, biosphere and hydrosphere. The accurate and precise determination of δ⁶⁵Cu in matrix reference materials is crucial in the effort to validate measurement methods. With the goal of expanding the number and variety of available geological and biological materials, we have characterised the δ⁶⁵Cu values of ten reference materials by MC‐ICP‐MS using C‐SSBIN model for mass bias correction. SGR‐1b (Green River shale), DOLT‐5 (dogfish liver), DORM‐4 (fish protein), TORT‐3 (lobster hepatopancreas), MESS‐4 (marine sediment) and PACS‐3 (marine sediment) have for the first time been characterised for δ⁶⁵Cu. Additionally, four reference materials (with published δ⁶⁵Cu values) have been characterised: BHVO‐1 (Hawaiian basalt), BIR‐1 (Icelandic basalt), W‐2a (diabase) and Seronorm? Trace Elements Serum L‐1 (human serum). The reference materials measured in this study possess complex and varied matrices with copper mass fractions ranging from 1.2 µg g^?1 to 497 µg g^?1 and δ⁶⁵Cu values ranging from ?0.20‰ to 0.52‰ with a mean expanded uncertainty of ± 0.07‰ (U, k = 2), covering much of the natural copper isotope variability observed in the environment.     

Sedimentary recycling in arc magmas: geochemical and U–Pb–Hf–O constraints on the Mesoproterozoic Suldal Arc, SW Norway

The Hardangervidda-Rogaland Block within southwest Norway is host to ~1.52 to 1.48 Ga continental building and variable reworking during the ~1.1 to 0.9 Ga Sveconorwegian orogeny. Due to the lack of geochronological and geochemical data, the timing and tectonic setting of early Mesoproterozoic magmatism has long been ambiguous. This paper presents zircon U–Pb–Hf–O isotope data combined with whole-rock geochemistry to address the age and petrogenesis of basement units within the Suldal region, located in the centre of the Hardangervidda-Rogaland Block. The basement comprises variably deformed grey gneisses and granitoids that petrologically and geochemically resemble mature volcanic arc lithologies. U–Pb ages confirm that magmatism occurred from ~1,521 to 1,485 Ma, and conspicuously lack any xenocrystic inheritance of distinctly older crust. Hafnium isotope data range from εHf_(initial) +1 to +11, suggesting a rather juvenile magmatic source, but with possible involvement of late Palaeoproterozoic crust. Oxygen isotope data range from mantle-like (δ¹⁸O ~5 ‰) to elevated (~10 ‰) suggesting involvement of low-temperature altered material (e.g., supracrustal rocks) in the magma source. The Hf–O isotope array is compatible with mixing between mantle-derived material with young low-temperature altered material (oceanic crust/sediments) and older low-temperature altered material (continent-derived sediments). This, combined with a lack of xenoliths and xenocrysts, exposed older crust, AFC trends and S-type geochemistry, all point to mixing within a deep-crustal magma-generation zone. A proposed model comprises accretion of altered oceanic crust and the overlying sediments to a pre-existing continental margin, underthrusting to the magma-generation zone and remobilisation during arc magmatism. The geodynamic setting for this arc magmatism is comparable with that seen in the Phanerozoic (e.g., the Sierra Nevada and Coast Range batholiths), with compositions in the Suldal Sector reaching those of average upper continental crust. As within these younger examples, factors that drive magmatism towards the composition of the average continental crust include the addition of sedimentary material to magma source regions, and delamination of cumulate material. Underthrusting of sedimentary materials and their subsequent involvement in arc magmatism is perhaps a more widespread mechanism involved in continental growth than is currently recognised. Finally, the Suldal Arc magmatism represents a significant juvenile crustal addition to SW Fennoscandia.     

Natural speciation of nickel at the micrometer scale in serpentine (ultramafic) topsoils using microfocused X-ray fluorescence,diffraction, and absorption

Serpentine soils and ultramafic laterites develop over ultramafic bedrock and are important geological materials from environmental, geochemical, and industrial standpoints. They have naturally elevated concentrations of trace metals, such as Ni, Cr, and Co, and also high levels of Fe and Mg. Minerals host these trace metals and influence metal mobility. Ni in particular is an important trace metal in these soils, and the objective of this research was to use microscale (µ) techniques to identify naturally occurring minerals that contain Ni and Ni correlations with other trace metals, such as Fe, Mn, and Cr. Synchrotron based µ-XRF, µ-XRD, and µ-XAS were used. Ni was often located in the octahedral layer of serpentine minerals, such as lizardite, and in other layered phyllosilicate minerals with similar octahedral structure, such as chlorite group minerals including clinochlore and chamosite. Ni was also present in goethite, hematite, magnetite, and ferrihydrite. Goethite was present with lizardite and antigorite on the micrometer scale. Lizardite integrated both Ni and Mn simultaneously in its octahedral layer. Enstatite, pargasite, chamosite, phlogopite, and forsterite incorporated various amounts of Ni and Fe over the micrometer spatial scale. Ni content increased six to seven times within the same 500 µm µ-XRD transect on chamosite and phlogopite. Data are shown down to an 8 µm spatial scale. Ni was not associated with chromite or zincochromite particles. Ni often correlated with Fe and Mn, and generally did not correlate with Cr, Zn, Ca, or K in µ-XRF maps. A split shoulder feature in the µ-XAS data at 8400 eV (3.7 Å^?1 in k-space) is highly correlated (94% of averaged LCF results) to Ni located in the octahedral sheet of layered phyllosilicate minerals, such as serpentine and chlorite-group minerals. A comparison of bulk-XAS LCF to averaged µ-XAS LCF results showed good representation of the bulk soil via the µ-XAS technique for two of the three soils. In the locations analyzed by µ-XAS, average Ni speciation was dominated by layered phyllosilicate and serpentine minerals (76%), iron oxides (18%), and manganese oxides (9%). In the locations analyzed by µ-XRD, average Ni speciation was dominated by layered phyllosilicate, serpentine, and ultramafic-related minerals (71%) and iron oxides (17%), illustrating the complementary nature of these two methods.

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Food habits and distribution of wintering canvasbacks,Aythya valisineria,on Chesapeake Bay

Baltic clams (Macoma balthica) were the predominant food items of 323 canvasbacks (Aythya valisineria) collected throughout Chesapeake Bay during 1970–1979. Natural vegetation constituted 4% of the food volume. Widgeongrass (Ruppia maritima) and redhead grass (Potamogeton perfoliatus) constituted the greatest percent volume and frequency of occurrence among the plant species, whereas wild celery (Vallisneria americana) constituted only a trace of the food volume. These results contrast with historical records of food habits of canvasbacks in Chesapeake Bay. Canvasback population estimates during the 1970’s were examined to detect annual and seasonal changes in distribution. Linear regression analyses of winter canvasback populations in the bay showed a significant decline in the upper-bay and middle-bay populations, but no significant changes in the lower-bay and Potomac River populations. The changes in winter distribution and abundance of the canvasback appear related to changes in natural food availability, which is the result of altered environmental conditions.     

Initiation of large-volume silicic centers in the Yellowstone hotspot track: insights from H<Subscript>2</Subscript>O- and F-rich quartz-hosted rhyolitic melt inclusions in the Arbon Valley Tuff of the Snake River Plain

During the onset of caldera cluster volcanism at a new location in the Snake River Plain (SRP), there is an increase in basalt fluxing into the crust and diverse silicic volcanic products are generated. The SRP contains abundant and compositionally diverse hot, dry, and often low-δ¹⁸O silicic volcanic rocks produced through time during the formation of individual caldera clusters, but more H₂O-rich eruptive products are rare. We report analyses of quartz-hosted melt inclusions from pumice clasts from the upper and lower Arbon Valley Tuff (AVT) to gain insight into the initiation of caldera cluster volcanism. The AVT, a voluminous, caldera-forming rhyolite, represents the commencement of volcanism (10.44 Ma) at the Picabo volcanic field of the Yellowstone hotspot track. This is a normal δ¹⁸O rhyolite consisting of early and late erupted members (lower and upper AVT, respectively) with extremely radiogenic Sr isotopes and unradiogenic Nd isotopes, requiring that ~50 % of the mass of these elements is derived from melts of Archean upper crust. Our data reveal distinctive features of the early erupted lower AVT melt including: variable F concentrations up to 1.4 wt%, homogenous and low Cl concentrations (~0.08 wt%), H₂O contents ranging from 2.3 to 6.4 wt%, CO₂ contents ranging from 79 to 410 ppm, and enrichment of incompatible elements compared to the late erupted AVT, subsequent Picabo rhyolites, SRP rhyolites, and melt inclusions from other metaluminous rhyolites (e.g., Bishop Tuff, Mesa Falls Tuff). We couple melt inclusion data with Ti measurements and cathodoluminescence (CL) imaging of the host quartz phenocrysts to elucidate the petrogenetic evolution of the AVT rhyolitic magma. We observe complex and multistage CL zoning patterns, the most critical being multiple truncations indicative of several dissolution–reprecipitation episodes with bright CL cores (higher Ti) and occasional bright CL rims (higher Ti). We interpret the high H₂O, F, F/Cl, and incompatible trace element concentrations in the context of a model involving melting of Archean crust and mixing of the crustal melt with basaltic differentiates, followed by multiple stages of fractional crystallization, remelting, and melt extraction. This multistage process, which we refer to as distillation, is further supported by the complex CL zoning patterns in quartz. We interpret new Δ¹⁸O(Qz-Mt) isotope measurements, demonstrating a 0.4 ‰ or ~180 °C temperature difference, and strong Sr isotopic and chemical differences between the upper and lower AVT to represent two separate eruptions. Similarities between the AVT and the first caldera-forming eruptions of other caldera clusters in the SRP (Yellowstone, Heise and Bruneau Jarbidge) suggest that the more evolved, lower-temperature, more H₂O-rich rhyolites of the SRP are important in the initiation of a caldera cluster during the onset of plume impingement.     

A temperature-induced reversible transformation between paratacamite and herbertsmithite

The crystal chemistry of paratacamite has been re-evaluated by studying a crystal from the holotype specimen BM86958 of composition Cu_3.71Zn_0.29(OH)₆Cl₂ using single-crystal X-ray diffraction at 100, 200, 300, 353, 393 and 423 K. At 300 K paratacamite has space group $R\bar{3}$ with unit-cell parameters a 13.644 and c 14.035 Å and exhibits a pronounced subcell, a′ = ½a and c′ = c, analogous to that of the closely related mineral herbertsmithite, Cu₃Zn(OH)₆Cl₂. Between 353 and 393 K, paratacamite undergoes a reversible phase transformation to the herbertsmithite-like substructure, space group $R\bar{3}m$ , unit-cell parameters a 6.839 and c 14.072 Å (393 K). The transformation is characterised by a gradual reduction in intensity of superlattice reflections, which are absent at 393 and 443 K. On cooling from 443 to 300 K at ~10 K min^?1, the superlattice reflections reappear and the refined structures ( $R\bar{3}$ ) of the initial and recovered 300 K states are almost identical. The complete reversibility of the transformation establishes that paratacamite of composition Cu_3.71Zn_0.29(OH)₆Cl₂ is thermodynamically stable at ambient temperatures. The nature of the rhombic distortion of the M(2)O₆ octahedron is discussed by considering two possibilities that are dependent upon the nature of cation substitution in the interlayer sites.     

Vacuum chambers for use in resin impregnation of core samples

The University of Alabama, Office of Archeological Services (OAS), through funding provided by a private corporation, began a research project aimed at a relatively noninvasive investigation of Mound R at Moundville Archaeological Park, Moundville, Alabama (Site 1Tu500). Plans for the project began in June 1997 with field investigations set for the following fall. In cooperation with Energen Corporation of Alabama, funding was developed for a ground penetrating radar (GPR) survey of the mound, as well as the recovery of 60 core samples from 12 coring locations on the summit of Mound R. Several of the core samples were selected by OAS for resin impregnation and microanalysis. With this goal in mind, OAS found it necessary to construct a vacuum chamber large enough to incorporate the samples. Its construction may be beneficial to others requiring larger chambers for similar analysis. © 1999 John Wiley & Sons, Inc.     

Carbonatite metasomatized peridotite xenoliths from southern Patagonia: implications for lithospheric processes and Neogene plateau magmatism

The mineral chemistry, major and trace element, and Sr–Nd isotopic composition of Cr-diopside, spinel peridotite xenoliths from the Estancia Lote 17 locality in southern Patagonia document a strong carbonatitic metasomatism of the backarc continental lithosphere. The Lote 17 peridotite xenolith suite consists of hydrous spinel lherzolite, wehrlite, and olivine websterite, and anhydrous harzburgite and lherzolite. Two-pyroxene thermometry indicates equilibration temperatures ranging from 870 to 1015 °C and the lack of plagioclase or garnet suggests the xenoliths originated from between ˜40 and 60 km depth. All of the xenoliths are LILE- and LREE-enriched, but have relatively low ⁸⁷Sr/⁸⁶Sr (0.70294 to 0.70342) and high ɛ_Nd (+3.0 to +6.6), indicating recent trace element enrichment (∼25 Ma, based on the low ⁸⁷Sr/⁸⁶Sr and high Rb concentrations of phlogopite separates) in the long-term, melt-depleted Patagonian lithosphere. Lote 17 peridotite xenoliths are divided into two basic groups. Group 1 xenoliths consist of fertile peridotites that contain hydrous phases (amphibole ± phlogopite ± apatite). Group 1 xenoliths are further subdivided into three groups (a, b, and c) based on distinctive textures and whole-rock chemistry. Group 1 xenolith mineralogy and chemistry are consistent with a complex metasomatic history involving variable extents of recent carbonatite metasomatism (high Ca/Al, Nb/La, Zr/Hf, low Ti/Eu) that has overprinted earlier metasomatic events. Group 2 xenoliths consist of infertile, anhydrous harzburgites and record cryptic metasomatism that is attributed to CO₂-rich fluids liberated from Group 1 carbonatite metasomatic reactions. Extremely variable incompatible trace element ratios and depleted Sr–Nd isotopic compositions of Lote 17 peridotite xenoliths indicate that the continental lithosphere was neither the primary source nor an enriched lithospheric contaminant for Neogene Patagonian plateau lavas. Neogene plateau magmatism associated with formation of asthenospheric slab windows may have triggered this occurrence of “intraplate-type” carbonatite metasomatism in an active continental backarc setting. Received: 26 January 2000 / Accepted: 1 March 2000