Small-volume Lu-Hf and U-Pb isotope determination of complex zircons by solution and laser ablation MC-ICP-MS

This study presents solution and laser ablation analysis methods suited to the determination of the Lu-Hf and U-Pb isotope signatures of small volumes of zircon corresponding to sub-nanogram amounts of Hf. A reduced-volume approach to laser ablation is taken with consecutive U-Pb and Lu-Hf isotopic analyses resulting in a total pit depth of 18 μm using a 25 μm laser ablation spot. This results in excavation of ~ 40 ng of zircon, equating to ~ 0.3 ng of Hf and uncertainties ~ 1 εHf (2s). The laser technique presented here is ideally suited to complex, finely-zoned zircons for which drilling to depth would intersect different zones. The possibility of reducing the total laser ablation pit depth to ~ 10 μm is demonstrated by decreasing the integration time for Hf isotope analysis without serious compromise of the uncertainty. Furthermore, the capability to determine the Hf isotope composition of the same amount of Hf using solution MC-ICP-MS is also demonstrated, as is the suitability of analyzing solutions not subject to Hf-HREE separation. For both solution and laser ablation methods, this study investigates possible methods of Yb interference correction, the potential for matrix effects, and the accurate determination of 176Lu/177Hf. Using the approaches described here, acceptable uncertainty levels are achieved to resolve complexity at the level of 25 × 18 μm (diameter × depth), and therefore this method has the potential to yield geologically meaningful results for rocks containing complexly-zoned zircons

Geochemical evidence of Milankovitch cycles in Atlantic Ocean ferromanganese crusts

Hydrogenetic ferromanganese crusts are considered a faithful record of the isotopic composition of seawater influenced by weathering processes of continental masses. Given their ubiquitous presence in all oceans of the planet at depths of 400–7000 meters, they form one of the most well-distributed and accessible records of water-mass mixing and climate. However, their slow accumulation rate and poor age constraints have to date limited their use to explore 100 ka paleoclimatic phenomena. Here it is shown how the Pb isotope signature and major element content of a Fe-Mn crust from the north-east Atlantic responded to changes in the intensity and geographic extent of monsoonal rainfall over West Africa, as controlled by climatic precession during the Paleocene. The studied high-spatial resolution (4 μm) laser-ablation multi-collector inductively coupled plasma mass spectrometer (LA-MC-ICP-MS) Pb isotope data is a nearly 2 order of magnitude improvement in spatial and temporal resolution compared to micro-drill subsamples. The record demonstrates cyclicity of the 206Pb/204Pb and 208, 207Pb/206Pb ratios at the scale of single Fe-Mn oxide laminae, in conjunction with variations in the Fe/Mn ratio, Al, Si and Ti content. Time-frequency analysis and astronomical tuning of the Pb isotope data demonstrates the imprint of climatic precession (∼20 ka) modulated by eccentricity (∼100 and 405 ka), yielding growth rates of 1.5–3.5 mm/Ma consistent with previous chemostratigraphic age models. In this context, boreal summer at the perihelion causes stronger insolation over West Africa, resulting in more intense and geographically extended monsoonal rainfalls compared to aphelion boreal summer conditions. This, in turn, influences the balance between the weathering endmembers feeding the north-east Atlantic basin. These results provide a new approach for calibrating Fe-Mn crust records to astronomical solutions, and allow their isotopic and chemical archive to be exploited with an improved temporal resolution of 1000–5000 years

The 1.23 Ga Fjellhovdane rhyolite, Grøssæ-Totak; a new age within the Telemark supracrustals, southern Norway

The Grøssæ-Totak supracrustal belt is part of the several-kilometre thick Telemark supracrustal sequences that are exposed in southern Norway. Deposition of the Telemark supracrustals spans the period between Telemarkian continental growth at ~1.52-1.48 Ga and Sveconorwegian orogenesis associated with continental collision at ~1.1-0.9 Ga. The timing of deposition is largely constrained by U-Pb geochronology of detrital zircons in sedimentary units, and igneous zircons within felsic volcanics. A younger Supergroup that has been referred to as the Sveconorwegian Supergroup comprises depositional ages younger than 1.16 Ga; units of the Grøssae-Totak belt have been mapped as part of this Supergroup. This study presents a new U-Pb age of 1233 ± 29 Ma for the Fjellhovdane rhyolite, one of the lowermost units within the Grøssæ-Totak belt; this age suggests that at least the lower part of this sequence is not part of the Sveconorwegian Supergroup, but formed in an earlier volcano-sedimentary basin that is correlative in age to the Sæsvatn-Valldal and Setesdal supracrustal belts that occur to the west and south respectively. The geochemistry of the Fjellhovdane rhyolite is compatible with crustal melting of previously-formed supra-subduction rocks, as has been advocated for the Sæsvatn-Valldal rhyolites

Tracking the evolution of the Grenvillian foreland basin: constraints from sedimentology and detrital zircon and rutile in the Sleat and Torridon groups, Scotland

The Grenville Orogen, although occupying a key position in the Rodinia supercontinent, lacks a clear foreland basin in its type area in eastern Canada. Early Neoproterozoic siliciclastic rocks in northern Scotland, however, are now interpreted as remnants of a proximal Grenvillian foreland basin. Analysis of the sedimentology and detrital zircon and rutile of the Torridon and underlying Sleat groups provide new constraints on the evolution of this basin. Youngest U-Pb detrital zircon grains yield ages of 1070–990 Ma in both groups, consistent with a Grenvillian source. The proportions of older age components vary throughout the stratigraphy. The lower Sleat Group shows a dominant ca. 1750 Ma peak, likely derived from local Rhinnian rocks in Scotland and Ireland uplifted within the Grenville Orogen. In the upper Sleat Group and Torridon Group, detrital zircon peaks at ca. 1650 Ma and ca. 1500–1100 Ma become increasingly important. These latter peaks correspond with Labradorian Pinwarian, Elzevirian and early Grenvillian protolith ages within the eastern Grenville Province in Canada, and reflect exhumation and erosion of different mid-crustal complexes within that sector of the orogen. There is no difference in detrital zircon ages across the low-angle Sleat/Torridon unconformity. Detrital rutile in the Torridon Group yields a significant ca. 1070 Ma, Grenville-age peak, but older grains (1700–1200 Ma) also occur, suggesting derivation from the cool (T < 600 °C) upper orogenic crust. The detrital mineral data and sedimentology suggest the following evolution of the Grenvillian foreland basin in Scotland: i) early deposition in a narrow marine foreland basin (lower Sleat Group), sourced from the Irish-Scottish sector of the Grenville Orogen, with orogen-normal fill; ii) within the narrow Sleat Group basin a gradual switch to more distal sources in the Canadian sector of the Grenville Orogen, via axial transport; iii) an abrupt switch in basin dynamics (but not in source) across the Sleat-Torridon boundary to fluvial braidplain deposition in a much wider, Torridon-Morar basin; iv) followed by a gradual retrogradation of that basin. The Torridon-Morar groups represent a major denudational event of the Grenville Orogen that we infer was linked to more distal deposits in East Greenland, Svalbard and Norway

Advances in Isotope Ratio Determination by LA–ICP–MS

LA–ICP–MS has proven to be an extremely important analytical tool within the Earth, environmental, and archaeological sciences. New developments in both instrumentation and methodology now provide the ability to extract age and isotopic tracer information in situ at a variety of scales (from nm to cm), in 2- and 3-dimensions, quickly and cost-effectively, providing considerable analytical flexibility compared to other micro-analytical techniques. Here, we review the current state of the art in laser ablation isotope ratio determination and provide some insights into future developments

Geochronology and structure of the eastern margin of the Tanzania Craton east of Dodoma

The precise position, nature and U-Pb zircon geochronology of the eastern margin of the Tanzania Craton has been studied in the Mpwapwa area, some 60 km east of Dodoma, central Tanzania, in a number of field transects over a ca. 45 km strike length of the craton margin. The rocks to the east of the Tanzania Craton in this area either belong to the Palaeoproterozoic Usagaran belt, or the “Western Granulite” terrane of the Neoproterozoic East African Orogen, according to different authors. The eastern part of the craton is underlain by typical Neoarchaean migmatitic grey granodioritic orthogneisses dated by ICP-MS at 2674 ± 73 Ma. There is a gradual increase in strain eastwards in these rocks, culminating in a 1 to 2 km wide, locally imbricated, ductile thrust/shear zone with mylonites indicating an oblique top-to-the-NW, transpressional sense of movement. East of the craton-edge shear zone, a series of high-grade supracrustal rocks are termed the “Mpwapwa Group”, in view of uncertain age and regional lithostratigraphic correlations. There is an apparent east-west lithological zonation of Mpwapwa Group parallel to the craton margin shear zone. In the west, immediately adjacent to the craton, the group consists of typical “shelf facies” metasediments (marbles, calc-silicates, quartzites etc.). U-Pb dating of detrital zircons from two Mpwapwa Group quartzite samples from this marginal zone contain only Archaean detritus, constraining their maximum depositional age to > ca. 2.6 Ga and suggesting that the group is Neoarchaean in age. The shelf rocks pass eastwards into garnet and kyanite-bearing semi-pelitic gneisses interlayered with bimodal mafic-felsic gneisses, where the mafic amphibolite gneisses may represent meta-basalts and the felsic rocks may have meta-rhyolite, -granite or –psammite protoliths. Massive garnet-clinopyroxene amphibolite layers in the Mpwapwa Group gneisses may have been intrusive mafic sills and possibly correlate with the Palaeoproterozoic Isimani Suite, which outcrops south of the study area and includes 2 Ga eclogites. Zircons from a quartzo-feldsapthic gneiss sample from the bimodal gneisses were dated and showed it to be a probable Neoarchaean rock which underwent metamorphism during the Palaeoproterozoic Usagaran event at ca. 1950 Ma. This event was broadly coeval with subduction, closure of an ocean basin and eclogite formation further south and led to the initial juxtaposition of the two Archaean blocks. The metamorphism probably dates the tectonic event when the Archaean Mpwapwa Group rocks were juxtaposed against the orthogneissic Tanzania Craton. The Mpwapwa Group was intruded by weakly foliated biotite granite at 1871 ± 35 Ma. Zircons in the granite have metamorphic rims dated between 550 and 650 Ma that grew during the East African orogenic event

Insights into the transfer of silicon isotopes into the sediment record

The first δ30Sidiatom data from lacustrine sediment traps are presented from Lake Baikal, Siberia. Data are compared with March surface water (upper 180 m) δ30SiDSi compositions for which a mean value of +2.28‰ ±  0.09 (95 % confidence) is derived. This value acts as the pre-diatom bloom baseline silicic acid isotopic composition of waters (δ30SiDSi initial). Open traps were deployed along the depth of the Lake Baikal south basin water column between 2012 and 2013. Diatom assemblages display a dominance ( > 85 %) of the spring/summer bloom species Synedra acus var radians, so that δ30Sidiatom compositions reflect predominantly spring/summer bloom utilisation. Diatoms were isolated from open traps and, in addition, from 3-monthly (sequencing) traps (May, July and August 2012) for δ30Sidiatom analyses. Mean δ30Sidiatom values for open traps are +1.23‰ ±  0.06 (at 95 % confidence and MSWD of 2.9, n = 10). Total dry mass sediment fluxes are highest in June 2012, which we attribute to the initial export of the dominant spring diatom bloom. We therefore argue that May δ30Sidiatom signatures (+0.67‰ ±  0.06, 2σ) when compared with mean upper water δ30SiDSi initial (e.g. pre-bloom) signatures can be used to provide a snapshot estimation of diatom uptake fractionation factors (ϵuptake) in Lake Baikal. A ϵuptake estimation of −1.61 ‰ is therefore derived, although we emphasise that synchronous monthly δ30SiDSi and δ30Sidiatom data would be needed to provide more robust estimations and therefore more rigorously test this, particularly when taking into consideration any progressive enrichment of the DSi pool as blooms persist. The near-constant δ30Sidiatom composition in open traps demonstrates the full preservation of the signal through the water column and thereby justifies the use and application of the technique in biogeochemical and palaeoenvironmental research. Data are finally compared with lake sediment core samples, collected from the south basin. Values of +1.30‰ ±  0.08 (2σ) and +1.43‰ ±  0.13 (2σ) were derived for cores BAIK13-1C (0.6–0.8 cm core depth) and at BAIK13-4F (0.2–0.4 cm core depth) respectively. Trap data highlight the absence of a fractionation factor associated with diatom dissolution (ϵdissolution) (particularly as Synedra acus var radians, the dominant taxa in the traps, is very susceptible to dissolution) down the water column and in the lake surface sediments, thus validating the application of δ30Sidiatom analyses in Lake Baikal and other freshwater systems, in palaeoreconstructions

‘Blind time’ – current limitations on laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) for ultra-transient signal isotope ratio analysis and application to individual sub-micron sized uranium particles

The application of laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) to the isotope ratio analysis of UOx particles has the potential to improve the isotopic determination of these particles when compared to currently utilised ICP-MS techniques. To investigate this a high-speed, integrated ablation cell and dual concentric injector design was tested in the expectation that the resulting increase in signal to noise ratio and sample ion yield would improve the determination of 234U/238U, 235U/238U and 236U/238U for such materials. However, when compared to a slower washout, more established low-volume cell design, the highly transient signals of the new design proved challenging for the mixed detector array of the multi-collector mass spectrometer, introducing a new bias. We describe a major component of this bias, referred to as ‘blind time’, and model its impact on UOx particle analysis. After accounting for blind time, average precisions for the uranium isotopic composition of sub-micron sized UOx particles using LA-MC-ICP-MS were 3% 1RSD for 235U/238U and 8% 1RSD for 234U/238U. When ablating a glass rather than a UOx particle, uncertainties of 1.3% 1RSD for 235U/238U were achieved for 150 nm equivalent particle sizes using LA-MC-ICP-MS

Geology, geochemistry and geochronology of the Songwe Hill carbonatite, Malawi

Songwe Hill, Malawi, is one of the least studied carbonatites but has now become particularly important as it hosts a relatively large rare earth deposit. The results of new mapping, petrography, geochemistry and geochronology indicate that the 0.8 km diameter Songwe Hill is distinct from the other Chilwa Alkaline Province carbonatites in that it intruded the side of the much larger (4 × 6 km) and slightly older (134.6 ± 4.4 Ma) Mauze nepheline syenite and then evolved through three different carbonatite compositions (C1–C3). Early C1 carbonatite is scarce and is composed of medium–coarse-grained calcite carbonatite containing zircons with a U–Pb age of 132.9 ± 6.7 Ma. It is similar to magmatic carbonatite in other carbonatite complexes at Chilwa Island and Tundulu in the Chilwa Alkaline Province and others worldwide. The fine-grained calcite carbonatite (C2) is the most abundant stage at Songwe Hill, followed by a more REE- and Sr-rich ferroan calcite carbonatite (C3). Both stages C2 and C3 display evidence of extensive (carbo)-hydrothermal overprinting that has produced apatite enriched in HREE (<2000 ppm Y) and, in C3, synchysite-(Ce). The final stages comprise HREE-rich apatite fluorite veins and Mn-Fe-rich veins. Widespread brecciation and incorporation of fenite into carbonatite, brittle fracturing, rounded clasts and a fenite carapace at the top of the hill indicate a shallow level of emplacement into the crust. This shallow intrusion level acted as a reservoir for multiple stages of carbonatite-derived fluid and HREE-enriched apatite mineralisation as well as LREE-enriched synchysite-(Ce). The close proximity and similar age of the large Mauze nepheline syenite suggests it may have acted as a heat source driving a hydrothermal system that has differentiated Songwe Hill from other Chilwa carbonatites