Method to Suppress Isobaric and Polyatomic Interferences for Measurements of Highly Siderophile Elements in Desilicified Geological Samples

Sample decomposition using inverse aqua regia at elevated temperatures and pressures (e.g., Carius tube or high‐pressure asher) is the most common method used to extract highly siderophile elements (HSEs: Ru, Rh, Pd, Re, Os, Ir, Pt and Au) from geological samples. Recently, it has been recognised that additional HF desilicification is necessary to better recover HSEs, potentially contained within silicate or oxide minerals in mafic samples, which cannot be dissolved solely by inverse aqua regia. However, the abundance of interfering elements tends to increase in the eluent when conventional ion‐exchange purification procedures are applied to desilicified samples. In this study, we developed an improved purification method to determine HSEs in desilicified samples. This method enables the reduction of the ratios of isobaric and polyatomic interferences, relative to the measured intensities of HSE isotope masses, to less than a few hundred parts per million. Furthermore, the total procedural blanks are either comparable to or lower than conventional methods. Thus, this method allows accurate and precise HSE measurements in mafic and ultramafic geological samples, without the need for interference corrections. Moreover, the problem of increased interfering elements, such as Zr for Pd and Cr for Ru, is circumvented for the desilicified samples

Sub-arc mantle enrichment in the Sunda rear-arc inferred from HFSE systematics in high-K lavas from Java

Many terrestrial silicate reservoirs display a characteristic depletion in Nb, which has been explained in some studies by the presence of reservoirs on Earth with superchondritic Nb/Ta. As one classical example, K-rich lavas from the Sunda rear-arc, Indonesia, have been invoked to tap such a high-Nb/Ta reservoir. To elucidate the petrogenetic processes active beneath the Java rear-arc and the causes for the superchondritic Nb/Ta in some of these lavas, we studied samples from the somewhat enigmatic Javanese rear-arc volcano Muria, which allow conclusions regarding the across-arc variations in volcanic output, source mineralogy and subduction components. We additionally report some data for an along-arc sequence of lavas from the Indonesian part of the Sunda arc, extending from Krakatoa in the west to the islands of Bali and Lombok in the east. We present major and trace element concentrations, Sr–Nd–Hf–Pb isotope compositions, and high-field-strength element (HFSE: Nb, Ta, Zr, Hf, W) concentrations obtained via isotope dilution and MC-ICP-MS analyses. The geochemical data are complemented by melting models covering different source compositions with slab melts formed at variable P–T conditions. The radiogenic isotope compositions of the frontal arc lavas in combination with their trace element systematics confirm previously established regional variations of subduction components along the arc. Melting models show a clear contribution of a sediment-derived component to the HFSE budget of the frontal arc lavas, particularly affecting Zr–Hf and W. In contrast, the K-rich rear-arc lavas tap more hybrid and enriched mantle sources. The HFSE budget of the rear-arc lavas is in particular characterized by superchondritic Nb/Ta (up to 25) that are attributed to deep melting involving overprint by slab melts formed from an enriched garnet–rutile-bearing eclogitic residue. Sub-arc slab melting was potentially triggered along a slab tear beneath the Sunda arc, which is the result of the forced subduction of an oceanic basement relief ~ 8 Myr ago as confirmed by geophysical studies. The purported age of the slab tear coincides with a paucity in arc volcanism, widespread thrusting of the Javanese basement crust as well as the short-lived nature of the K-rich rear-arc volcanism at that time. © 2021, The Author(s)

A Mesoarchean Large Igneous Province on the Eastern Kaapvaal Craton (Southern Africa) Confirmed by Metavolcanic Rocks from Kubuta, Eswatini

Mesoarchean magmatism is widespread on the eastern margin of the Kaapvaal Craton, but its origin is still poorly understood, mainly because geochemical data is rare. To shed some light on the source of this Mesoarchean magmatism and to relate different Mesoarchean volcanic sequences to each other, we provide major and trace element data as well as Hf-Nd isotope compositions of amphibolites sampled close to the Kubuta Ranch in south-central Eswatini. These amphibolites, so far, were of unknown correlation to any volcanic sequence in Eswatini or South Africa. Hence, the aim of our study is to characterize the mantle source composition of these volcanic rocks and, furthermore, to constrain their genetic relation to other volcanic sequences in Eswatini and South Africa. Our findings reveal that, based on coherent trace element patterns and similar Nd isotope characteristics, the Kubuta volcanic rocks can be genetically linked to the ca. 3.0 Ga Usushwana Igneous Complex in West-Central Eswatini and the ca. 2.9 Ga Hlagothi Complex located in the KwaZulu-Natal province. In contrast, the coeval ca. 3.0 Ga Nsuze and ca. 2.9 Ga Mozaan Groups (Pongola Supergroup) of south-central Eswatini and northern KwaZulu-Natal province have slightly enriched compositions compared to the newly sampled Kubuta volcanic rocks. Our results suggest that the Nsuze and Mozaan Groups were sourced from a primitive mantle reservoir, whereas the Usushwana, Hlagothi, and Kubuta mafic rocks were derived by melting of a more depleted mantle source comparable to that of modern depleted MORB. Furthermore, our assimilation-fractional crystallization (AFC) calculations and Nd isotope constraints reveal that some samples were contaminated by the crust and that the crustal contaminants possibly represent felsic rocks related to the ca. 3.5 Ga crust-forming event in the Ancient Gneiss Complex. Alternatively, melting of a metasomatized mantle or plume-lithospheric mantle interaction may also produce the trace element and isotopic compositions observed in the samples. From a synthesis of our geochemical observations and age data from the literature, we propose a refined petrogenetic model, for a continental flood basalt setting in a Mesoarchean large igneous province on the eastern Kaapvaal Craton. Our petrogenetic model envisages two magma pulses sourced from a primitive mantle reservoir that led to the formation of the Nsuze (first) and Mozaan (second) lavas. Conductive heating of ambient depleted mantle by the mantle plumes caused partial melting that led to the formation of the Usushwana Igneous Complex associated with the first magmatic event (Nsuze) and the Hlagothi Igneous Complex associated with the second magmatic event (Mozaan). However, due to lacking age data of sufficient resolution, it is not possible to affiliate the Kubuta lavas to either the first or the second magmatic event

Mineralogical Controls on the Ti Isotope Composition of Subduction Zone Magmas

The positive Ti isotope versus SiO2-content correlation in igneous rocks reflects the fractional crystallization of Ti-bearing oxide minerals. However, Ti isotope variations of subduction-related igneous rocks indicate that the Ti isotope compositions of their mantle sources are heterogeneous and additional mineral phases may promote Ti isotope fractionation. We have determined the Ti isotope composition of well-characterized subduction-related basalts, andesites and boninites. Samples from the Solomon Islands, the Troodos ophiolite in Cyprus, and Cape Vogel in Papua New Guinea show small but resolvable variations that may be related to differences in their mantle sources. Specifically, the δ49Ti of boninites (+0.109‰ to +0.168‰) is slightly higher than that of tholeiites (−0.027‰ to +0.111‰) from the same localities (Troodos in Cyprus and Cape Vogel in Papua New Guinea). Modeling suggests the partial melting of progressively depleted mantle sources where residual Cr-spinel plays a greater role in controlling the Ti budget during partial melting. More pronounced variations in δ49Ti are clearly linked to the fractional crystallization of Ti-oxides: Samples from Rabaul Volcanic Complex (New Britain, Papua New Guinea) show increasing δ49Ti (up to +0.373‰) with increasing Ti/V and decreasing Dy/Yb. Fractional crystallization models suggest that oxide minerals and amphibole are needed to sufficiently increase the δ49Ti of these magmas. Our study highlights that the combination of diagnostic trace element patterns and Ti isotope compositions in subduction-related igneous rocks can be a powerful tool to constrain petrogenetic processes and to discriminate between different crystallizing mineral phases

Zircon M127 - A Homogeneous Reference Material for SIMS U-Pb Geochronology Combined with Hafnium, Oxygen and, Potentially, Lithium Isotope Analysis

In this article, we document a detailed analytical characterisation of zircon M127, a homogeneous 12.7 carat gemstone from Ratnapura, Sri Lanka. Zircon M127 has TIMS-determined mean U-Pb radiogenic isotopic ratios of 0.084743 ± 0.000027 for 206Pb/238U and 0.67676 ± 0.00023 for 207Pb/235U (weighted means, 2s uncertainties). Its 206Pb/238U age of 524.36 ± 0.16 Ma (95% confidence uncertainty) is concordant within the uncertainties of decay constants. The d18O value (determined by laser fluorination) is 8.26 ± 0.06‰ VSMOW (2s), and the mean 176Hf/177Hf ratio (determined by solution ICP-MS) is 0.282396 ± 0.000004 (2s). The SIMS-determined d7Li value is -0.6 ± 0.9‰ (2s), with a mean mass fraction of 1.0 ± 0.1 µg g-1 Li (2s). Zircon M127 contains ~ 923 µg g-1 U. The moderate degree of radiation damage corresponds well with the time-integrated self-irradiation dose of 1.82 × 1018 alpha events per gram. This observation, and the (U-Th)/He age of 426 ± 7 Ma (2s), which is typical of unheated Sri Lankan zircon, enable us to exclude any thermal treatment. Zircon M127 is proposed as a reference material for the determination of zircon U-Pb ages by means of SIMS in combination with hafnium and stable isotope (oxygen and potentially also lithium) determination

Разработка автоматизированной системы контроля и управления топливоподачей котельной ЛПДС «Никольское» на базе водогрейных котлов Турботерм-5000

Выпускная квалификационная работа 108 с., 7 рис., 24 табл., 17 источников, 3 приложения. Объектом исследования является котельная линейной производственно-диспетчерской станции "Никольское". Цель работы – разработка автоматизированной системы контроля и управления топливоподачей котельной ЛПДС "Никольское" на базе водогрейных котлов Турботерм-5000. В процессе исследования проводилась рахработка: 1) структурной схемы автоматизированной системы контроля и управления; 2) выбор необходимых технических средств измерений; 3) функциональной схемы автоматизированной системы контроля и управления; 4) принципиальной электрической схемы щита контроля и управления ; 5) комплекта конструкторской документации на щит контроля и управления. 6) разработка мнемосхемы.Final qualifying work 108 pp., 7 fig., 24 tab., 17 sources, 3 annexes. The object of research is a linear boiler production and control station "Nikolskoye". The purpose of work - development of an automated control system of fuel supply boiler LPDS "Nikolskoye" based boilers Turboterm-5000. The study was conducted rahrabotka: 1) block diagram of the automated control system; 2) the selection of the necessary technical means of measurement; 3) functional diagram of the automated control system; 4) schematic diagrams board monitoring and control; 5) set of design documentation for board control and management. 6) the development of the graphic

Late Cenozoic tephrostratigraphy offshore the southern Central American Volcanic Arc: 2. Implications for magma production rates and subduction erosion

Pacific drill sites offshore Central America provide the unique opportunity to study the evolution of large explosive volcanism and the geotectonic evolution of the continental margin back into the Neogene. The temporal distribution of tephra layers established by tephrochonostratigraphy in Part 1 indicates a nearly continuous highly explosive eruption record for the Costa Rican and the Nicaraguan volcanic arc within the last 8 M.y. The widely distributed marine tephra layers comprise the major fraction of the respective erupted tephra volumes and masses thus providing insights into regional and temporal variations of large-magnitude explosive eruptions along the southern Central American Volcanic Arc (CAVA). We observe three pulses of enhanced explosive magmatism between 0-1 Ma at the Cordillera Central, between 1-2 Ma at the Guanacaste and at >3 Ma at the Western Nicaragua segments. Averaged over the long-term the minimum erupted magma flux (per unit arc length) is ∼0.017 g/ms. Tephra ages, constrained by Ar-Ar dating and by correlation with dated terrestrial tephras, yield time-variable accumulation rates of the intercalated pelagic sediments with four prominent phases of peak sedimentation rates that relate to tectonic processes of subduction erosion. The peak rate at >2.3 Ma near Osa particularly relates to initial Cocos Ridge subduction which began at 2.91±0.23 Ma as inferred by the 1.5 M.y. delayed appearance of the OIB geochemical signal in tephras from Barva volcano at 1.42 Ma. Subsequent tectonic re-arrangements probably involved crustal extension on the Guanacaste segment that favored the 2-1 Ma period of unusually massive rhyolite production

Kimberlites reveal 2.5-billion-year evolution of a deep, isolated mantle reservoir

The widely accepted paradigm of Earth's geochemical evolution states that the successive extraction of melts from the mantle over the past 4.5 billion years formed the continental crust, and produced at least one complementary melt-depleted reservoir that is now recognized as the upper-mantle source of mid-ocean-ridge basalts1. However, geochemical modelling and the occurrence of high 3He/4He (that is, primordial) signatures in some volcanic rocks suggest that volumes of relatively undifferentiated mantle may reside in deeper, isolated regions2. Some basalts from large igneous provinces may provide temporally restricted glimpses of the most primitive parts of the mantle3,4, but key questions regarding the longevity of such sources on planetary timescales—and whether any survive today—remain unresolved. Kimberlites, small-volume volcanic rocks that are the source of most diamonds, offer rare insights into aspects of the composition of the Earth’s deep mantle. The radiogenic isotope ratios of kimberlites of different ages enable us to map the evolution of this domain through time. Here we show that globally distributed kimberlites originate from a single homogeneous reservoir with an isotopic composition that is indicative of a uniform and pristine mantle source, which evolved in isolation over at least 2.5 billion years of Earth history—to our knowledge, the only such reservoir that has been identified to date. Around 200 million years ago, extensive volumes of the same source were perturbed, probably as a result of contamination by exogenic material. The distribution of affected kimberlites suggests that this event may be related to subduction along the margin of the Pangaea supercontinent. These results reveal a long-lived and globally extensive mantle reservoir that underwent subsequent disruption, possibly heralding a marked change to large-scale mantle-mixing regimes. These processes may explain why uncontaminated primordial mantle is so difficult to identify in recent mantle-derived melts

Late Cenozoic tephrostratigraphy offshore the southern Central American Volcanic Arc: 1. Tephra ages and provenance

We studied the tephra inventory of 18 deep sea drill sites from six DSDP/ODP legs (Legs 84, 138, 170, 202, 205, 206) and two IODP legs (Legs 334 and 344) offshore the southern Central American Volcanic Arc (CAVA). Eight drill sites are located on the incoming Cocos plate and ten drill sites on the continental slope of the Caribbean plate. In total we examined ∼840 ash-bearing horizons and identified ∼650 of these as primary ash beds of which 430 originated from the CAVA. Correlations of ash beds were established between marine cores and with terrestrial tephra deposits, using major and trace element glass compositions with respect to relative stratigraphic order. As a prerequisite for marine-terrestrial correlations we present a new geochemical data set for significant Neogene and Quaternary Costa Rican tephras. Moreover, new Ar/Ar ages for marine tephras have been determined and marine ash beds are also dated using the pelagic sedimentation rates. The resulting correlations and provenance analyses build a tephrochronostratigraphic framework for Costa Rica and Nicaragua that covers the last >8 Myr. We define 39 correlations of marine ash beds to specific tephra formations in Costa Rica and Nicaragua; from the 4.15 Ma Lower Sandillal Ignimbrite to the 3.5 ka Rincón de la Vieja Tephra from Costa Rica, as well as another 32 widely distributed tephra layers for which their specific region of origin along Costa Rica and Nicaragua can be constrained