Determination of Major/ Minor and Trace Elements in Silicate Samples by ICP-QMS and ICP-SFMS Applying Isotope Dilution-Internal Standardisation (ID-IS) and Multi-Stage Internal Standardisation

A method for the determination of major, minor and trace elements in silicate samples by ICP‐QMS and ICP‐SFMS applying isotope dilution‐internal standardisation (ID‐IS) and multi‐stage internal standardisation has been developed. Samples with an enriched isotope of ¹⁴⁹Sm (spike) were decomposed by a HF/HCIO₄ mixture and stepwise drying and finally diluted. In ID‐IS for trace element analyses by Q‐pole type ICP‐MS (ICP‐QMS), the Sm concentration was determined by ID, while other trace elements (Li, Be, Rb, Sr, Y, In, Cs, Ba, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, Bi, Th and U) were determined using the ¹⁴⁹Sm intensity as an internal standard. Major and minor elements were determined by multi‐stage internal standardisation, with Na, Mg, Al, P, Ca, V, Mn, Fe and Co measured by sector magnetic field type ICP‐MS (ICP‐SFMS) at middle resolution (MR; M/AM =～ 3000) using Sr determined by ICP‐QMS in the sample as the internal standard. Potassium, Sc, Ni, Cu, Zn and Ga were measured at high resolution (HR; M/ΔM ～ 7500) using the Sr concentration obtained by ICP‐QMS or the Mn concentration obtained by ICP‐SFMS at MR as internal standard. The merit of ID‐IS is that accurate dilution of the sample is not required. Matrix effects on elemental ratios down to a dilution factor (DF) of 600 were not observed in either types of mass spectrometry. Pseudo‐flow injection (FI), where transient signals were integrated, was used in ICP‐QMS, while conventional continuous sample introduction was used in ICP‐SFMS, resulting in total required sample solutions of 0.026 ml and 0.08 ml, respectively. Detection limits were low enough to determine these elements in depleted ultramafic rocks, and typical reproducibilities for basalts were 3% (Li‐Be), 1% (Rb‐U), 5% (In, Tl and Bi), 7% (Sc‐Ga) and 3% (major elements). Carbonaceous chondrites including Orgueil (Cll), Murchison (CM2) and Allende (CV3), as well as reference materials, JB‐1, ‐2, ‐3, JA‐1, ‐2, ‐3 and JP‐1 (GSJ), BHVO‐1, AGV‐1, PCC‐1 and DTS‐1 (USGS), were analysed to show the applicability of this method. Une méthode permettant la détermination des éléments majeurs, mineurs et en trace dans les echantillons silicates par ICP‐QMS et ICP‐SFMS a été développée. Elle combine la standardisation interne par dilution isotopique (ID‐IS) et la standardisation interne en deux étapes. Les échantillons, auxquels est ajouté un spike enrichi en ¹⁴⁹ Sm, sont décomposés par une mixture HF/HCIO_4′ séchés progressivement puis dilués. Dans la phase de standardisation interne par dilution isotopique avec un ICP‐MS à quadrupôle (ICP‐QMS), la concentration en Sm est déterminée par dilution isotopique tandis que les autres éléments en trace (Li, Be, Rb, Sr, Y, In, Cs, Ba, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, Pb, Bi, Th et U) sont déterminés en utilisant le signal de ¹⁴⁹ Sm comme standard interne. Les éléments majeurs et mineurs sont déterminés par standardisation interne par étapes, avec Na, Mg, Al, P, Ca, V, Mn, Fe et Co mesurés par ICP‐MS à secteur magnétique (ICP‐SFMS) en résolution intermédiaire (MR; M/ΔM =～ 3000 en utilisant Sr, mesuré par ICP‐QMS comme standard interne. Les éléments K, Sc, Ni, Cu, Zn et Ga sont mesurés en Haute Résolution (M/ΔM ～ 7500) en utilisant comme standard interne, soit la concentration en Sr obtenue par ICP‐QMS soit la concentration en Mn obtenue par ICP‐SFMS en résolution moyenne. La technique de ID‐IS a l'avantage de ne pas nécessiter la connaissance exacte du facteur de dilution de l'Schantillon. Aucun effet de matrice sur la mesure de rapports élémentaires n'a été observé sur l'un ou l'autre des spectromètres de masse, ceci jusqu'à un facteur de dilution (DF) de 600. Les analyses par ICP‐QMS ont été effectuées par pseudo injection de flux (Fl) et intégration d'un signal transitoire tandis que les analyses par ICP‐SFMS l'ont été avec un système conventionnel d'introduction. Le volume total de solution d'échantillon nécessaire etait de 0.026 ml et 0.08 ml respectivement. Les limites de détection étaient suffisamment basses pour permettre la détermination de ces éléments dans des roches ultrabasiques et les reproductibilités pour les basaltes étaient de l'ordre de 3% (Li‐Be), 1 % (Rb‐U), 5% (In, Tl et Bi), 7% (Sc‐Ga) et 3% (tous les éléments majeurs). Des chondrites carbonées dont Orgueil (Cll), Murchison (CM2) et Allende (CV3) ainsi que des matériaux de référence JB‐1, ‐2, ‐3, JA‐1, ‐2, ‐3 et JP‐1 (GSJ), BHVO‐1, AGV‐1, PCC‐1 et DTS (USGS) ont été analysés pour démontrer l'applicabilité de la méthode.     

Origin and evolution of the Nakhla meteorite inferred from the Sm-Nd and U-Pb systematics and REE,Ba, Sr,Rb and K abundances

Analyses of Sm-Nd and U-Th-Pb systematics, REE, Ba, Sr, Rb and K concentrations were carried out for whole rock and mineral separates from the Nakhla meteorite. The 1.26 ±.07 b.y. Sm-Nd age obtained in this work is in good agreement with those previously obtained by the Rb-Sr and Ar-Ar methods. The high initial ?_Nd value of +16 suggests that Nakhla was derived from a light REE-depleted, old planetary mantle source. U-Th-Pb data, after correction for pre-analytical terrestrial Pb contamination assuming an age of 1.26 b.y., suggest that the age of the Nakhla source is ?4.33 b.y. The agreement in the age determined by three independent radiometric methods and the high initial ?_Nd value strongly suggest that the 1.3 b.y. age dates one thorough igneous event in the parent body which not only reset these isotopic systems but also established the chemical and petrologic characteristics observed for the Nakhla meteorite.Using a three-stage Sm-Nd evolution model in combination with LIL element data and estimated partition coefficients, we have tested partial melting and fractional crystallization models to estimate LIL element abundances in a possible Nakhla source. Our model calculations suggest that partial melting of the light REE-depleted source followed by extensive fractional crystallization (?50%) of the partial melt could account for the REE abundances in the Nakhla constituent minerals. The estimated source is depleted in the light REE, Ba, Rb and K and therefore may resemble the MORB source in the earth's upper mantle or the upper 60–300 km of the moon.The significantly younger age of Nakhla than the youngest lunar rock; the young differentiation age inferred from the U-Th-Pb data, and the estimated LIL element abundances (including those of K, U and Th) in the source suggest that the Nakhla meteorite may have been derived from a relatively large, well-differentiated planetary body such as Mars.     

Origin of felsic volcanism in the Izu arc intra-arc rift

An intra-arc rift (IAR) is developed behind the volcanic front in the Izu arc, Japan. Bimodal volcanism, represented by basalt and rhyolite lavas and hydrothermal activity, is active in the IAR. The constituent minerals in the rhyolite lavas are mainly plagioclase and quartz, whereas mafic minerals are rare and are mainly orthopyroxene without any hydrous minerals such as amphibole and biotite. Both the phenocryst and groundmass minerals have felsic affinities with a narrow compositional range. The petrological and bulk chemical characteristics are similar to those of melts from some partial melting experiments that also yield dry rhyolite melts. The hydrous mineral-free narrow mineral compositions and low-Al₂O₃ affinities of the IAR rhyolites are produced from basaltic middle crust under anhydrous low-temperature melting conditions. The IAR basalt lavas display prominent across-arc variation, with depleted elemental compositions in the volcanic front side and enriched compositions in the rear-arc side. The across-arc variation reflects gradual change in the slab-derived components, as demonstrated by decreasing Ba/Zr and Th/Zr values to the rear-arc side. Rhyolite lavas exhibit different across-arc variations in either the fluid-mobile elements or the immobile elements, such as Nb/Zr, La/Yb, and chondrite-normalized rare earth element patterns, reflecting that the felsic magmas had different source. The preexisting arc crust formed during an earlier stage of arc evolution, most probably during the Oligocene prior to spreading of the Shikoku back-arc basin. The lack of systematic across-arc variation in the IAR rhyolites and their dry/shallow crustal melting origin combines to suggest re-melting of preexisting Oligocene middle crust by heat from the young basaltic magmatism.     

Simultaneous Determination of Cd,In, Tl and Bi by Isotope Dilution‐Internal Standardisation ICP‐QMS with Corrections Using Externally Measured MoO+/Mo+ Ratios

A method for the simultaneous determination of Cd with In, Tl and Bi by isotope dilution‐internal standardisation (ID‐IS) ICP‐QMS using the same aliquot for rare earth element and other trace element determinations was developed. Samples mixed with an enriched ¹⁴⁹Sm spike were decomposed using a HF‐HClO₄ mixture, which was evaporated and then diluted with HNO₃. After determination of Sm by ID‐ICP‐QMS and Cd, In, Tl and Bi concentrations were determined using the ¹⁴⁹Sm intensity as an internal standard. The interference of MoO⁺ on Cd⁺ was corrected using the MoO⁺/Mo⁺ ratio separately measured using a Mo standard solution, and the validity of the externally determined oxide‐forming ratio correction was evaluated. The MoO⁺/Mo⁺ ratios measured using the standard solution and samples were ～ 0.0002 and < 0.002, respectively. Detection limits for Cd, In, Tl and Bi in silicate samples were at levels of < 1 ng g^?1 with a total uncertainty of < 7%. Cadmium in the carbonaceous chondrites, Orgueil (CI1), Murchison (CM2) and Allende (CV3) as well as Cd, In, Tl and Bi in the reference materials, JB‐2, JB‐3, JA‐1, JA‐2, JA‐3, JP‐1 (GSJ), BHVO‐1, AGV‐1, PCC‐1 and DTS‐1 (USGS) and NIST SRM 610, 612, 614 and 616 were determined to show the applicability of this method.     

Sequence-stratigraphic signatures of hemipelagic siltstones in deep-water successions: the Lower Pleistocene Kiwada and Otadai Formations, Boso Peninsula, Japan

Sequence-stratigraphic signatures of hemipelagic siltstones were investigated using profiles of the magnetic susceptibility and selected chemical composition of the Early Pleistocene deep-water successions of the Kiwada and Otadai Formations on the Boso Peninsula, Japan. In the context of an independently developed sequence-stratigraphic framework for the submarine-fan deposits of the Otadai Formation, the magnetic susceptibility and chemical composition, such as the concentrations of TiO₂, MgO and Fe₂O₃, show that the lowstand systems tract deposits have higher values of these parameters than the transgressive and highstand systems tract deposits. In contrast, the CaO contents have inverse relationships with the magnetic susceptibility and are higher in the transgressive and highstand systems tract deposits. The positions of sequence boundaries largely coincide with the horizons from which the magnetic susceptibility and the contents of mafic component increase abruptly. The sequence-stratigraphic variations in the magnetic susceptibility and chemical composition of the submarine-fan hemipelagic siltstones are due to increases in the input of fine-grained, terrigenous clastic sediments from midwater flow suspension, in addition to the direct fluvial supply of relatively unmodified terrigenous clastic sediments during relative sea-level lowstands, although grain size of hemipelagic siltstones does not exhibit any distinct variation through depositional sequences. The Kiwada Formation is characterized by siltstone-dominated basin-plain deposits and its sequence-stratigraphic classification has been difficult when using just lithofacies features. Nevertheless, the profiles of the magnetic susceptibility and chemical composition of the basin-plain deposits are similar to those of the submarine-fan deposits with duration largely equivalent to the 41,000-years obliquity cycle of the Early Pleistocene oxygen isotope sea-level index. This finding indicates that the profiles of the magnetic susceptibility and chemical composition of hemipelagic siltstones reflect sequence-stratigraphic variation in the input of fine-grained terrigenous clastic sediments to the deep-water environments and are crucial for the recognition of cryptic sequence boundaries in hemipelagic successions.     

Impact of the winter North Atlantic Oscillation (NAO) on the Western Pacific (WP) pattern in the following winter through Arctic sea ice and ENSO: part I—observational evidence

Climate Dynamics - On the basis of a 51-year statistical analysis of reanalysis data, we propose for the first time that the positive phase of the Western Pacific (WP) pattern in the winter is...     

Short-term and intermediate-term geochemical precursors

Detection of precursory phenomena in observation data is essential to earthquake prediction studies. Continuous monitoring of radon concentration in groundwater in Japan in one case showed a short-term anomaly related to a nearby earthquake. With the exception of the 1978 Izu-Oshimakinkai earthquake (M7.0), however, no abnormal change has been noted. This may be due partially to difficulty in detecting insignificant precursory signals from observation data, which ordinarily contains a noise-induced fluctuations, and partially to lack of understanding of the mechanism controlling the appearance of precursory phenomena. In order to increase our knowledge of the variation pattern of precursory changes in radon concentration of groundwater, hydrologic precursors with significant features are examined in this paper. Complexity of appearance of precursory phenomena and problems in assignment of the specific earthquake are discussed.     

Growth characteristics ofChattonella antiqua

Nutrient requirements of a red tide flagellate,Chattonella antiqua, were investigated in a laboratory culture experiment. Growth ofC. antiqua was supported by nitrate and ammonium, and by urea to a limited extent, but not by glycine, alanine and glutamate. Orthophosphate served as a good phosphorus source but glycerophosphate did not. Fe³⁺ (1µM) fully promoted the flagellate's growth in the presence of 80µM of EDTA. The addition of Mn²⁺ (0–20µM), Zn²⁺ (0–10µM) and Co²⁺ (0–0.4µM) did not show any effect. Among three vitamins tested, only B₁₂ (6 ng 1^?1) served as a growth factor. Glucose, acetate and glycolate did not improve growth in the light nor did they support growth in darkness. The minimum cell quotas for nitrogen, phosphorus, iron and B₁₂ were estimated to be 11 pmoles ce^?1, 1.0, ～0.09 and 1.1 fg cell^?1, respectively.     

Relative influence of biotic and abiotic processes on travertine fabrics,Satono‐yu hot spring,Japan

The relative influences of biotic and abiotic processes on travertine fabrics are still not well understood, despite increasing interest in the last decade to better understand the record of ancient microbial life and sedimentary fabrics in microbial hydrocarbon reservoirs. This study examines travertines at Satono‐yu hot spring in Japan (the temperature of water flowing over the travertine was ca 35°C), to better understand the interaction between depositional, hydrochemical and microbial parameters at different flow settings. Characteristics of the bulk hydrochemistry, mineralogy (exclusively aragonite) and the driving force for precipitation (primarily abiotic CO₂ degassing with some photosynthetic microbial contribution) were similar among all of the flow settings. Conversely, the increase in flow velocity suppressed the influence of photosynthesis and enhanced the abiotic precipitation due to the thinner diffusive boundary layer at the travertine surface–water interface. Additionally, the increase in flow velocity changed the microbial composition and decreased the bacterial diversity by reflecting their adhesion efficiency on the travertine substrate. The acidity of the cyanobacterial sheaths controls the aragonite nucleation rate and the resulting calcification, even at significantly high equilibrium CO₂ partial pressure (ca 22 to 28 matm), high dissolved inorganic carbon concentration (ca 35 to 38 mmol l^?1), and elevated aragonite saturation state (ca 20‐fold to 34‐fold). Therefore, the increase in flow velocity suppresses the microbial influence with respect to the increase in the saturation state, the nucleation site supply and pore space generation. Overall, this results in the predominance of abiotic precipitation under high flow velocities. Consequently, a sparse‐micritic fabric with abundant interlamina porosity forms under lower flow velocity where the microbial influence is effective, while a dense‐sparitic fabric with little inter‐crystalline porosity forms under higher flow velocity where abiotic precipitation prevails. These findings provide an essential base for assessing the formation processes of ancient travertines and comparable deposits from petrological fabrics.     

Correction to: Street-scale storm surge load impact assessment using fine-resolution numerical modelling: a case study from Nemuro,Japan

Natural Hazards - To: Street-scale storm.