Albany K-Feldspar: A New Pb Isotope Reference Material

Lead isotopes are a powerful and versatile tool to elucidate fundamental geological problems related to the formation and evolution of continental crust. K-feldspar is a popular target for Pb isotope measurement as it is prevalent in many rock types and tends to capture the initial Pb isotope composition of its parental magma. We present data for a new Pb isotope reference material: Albany K-feldspar; as well as updated data for Shap K-feldspar. Results of Pb double-spike TIMS for Albany K-feldspar are ²⁰⁶Pb/²⁰⁴Pb = 16.7872 ± 0.0062, ²⁰⁷Pb/²⁰⁴Pb = 15.5640 ± 0.0056, and ²⁰⁸Pb/²⁰⁴Pb = 36.6600 ± 0.0168 (2s). TIMS measurement results for Shap K-feldspar indicate two isotopically distinct Pb populations. LA-MC-ICP-MS, with a spatial resolution as high as 15 μm, indicates a homogeneous Pb isotopic composition in Albany K-feldspar. In accord with previous studies, our results show that scatter in the measured Pb isotope ratios, related to the low natural isotopic abundance of ²⁰⁴Pb, along with the effect of isobaric ²⁰⁴Hg-²⁰⁴Pb interference, increases at lower count rates. However, the mean Pb isotope ratios measured via LA-MC-ICP-MS using a range of spot sizes are in excellent agreement with TIMS results thus highlighting the feasibility of Pb isotope determination via LA-MC-ICP-MS to access geological information preserved in small crystals, including mineral inclusions.     

147Sm‐143Nd and 176Lu‐176Hf systematics of eucrite and angrite meteorites

Comparative planetary geochemistry provides insight into the origin and evolutionary paths of planetary bodies in the inner solar system. The eucrite and angrite achondrite groups are particularly interesting because they show evidence of early planetary differentiation. We present ¹⁴⁷Sm‐¹⁴³Nd and ¹⁷⁶Lu‐¹⁷⁶Hf analyses of eight noncumulate (basaltic) eucrites, two cumulate eucrites, and three angrites, which together place new constraints on the evolution and differentiation histories of the crusts of the eucrite and angrite parent bodies and their mantle mineralogies. The chemical compositions of both eucrites and angrites indicate similar evolutionary paths and petrogenetic models with formation and isolation of differentiated crustal reservoirs associated with segregation of ilmenite. We report a ¹⁴⁷Sm‐¹⁴³Nd mineral isochron age for the Moama cumulate eucrite of 4519 ± 34 Ma (MSWD = 1.3). This age indicates protracted magmatism within deep crustal layers of the eucrite parent body lasting up to about 50 Ma after the formation of the solar system. We further demonstrate that the isotopic compositions of constituent minerals are compromised by secondary processes hindering precise determination of mineral isochron ages of basaltic eucrites and angrites. We interpret the changes in geochemistry and, consequently, the erroneous ¹⁴⁷Sm‐¹⁴³Nd and ¹⁷⁶Lu‐¹⁷⁶Hf internal mineral isochron ages of basaltic eucrites and angrites as the result of metamorphic events such as impacts (effects from pressure, temperature, and peak shock duration) on the surfaces of the eucrite and angrite parent bodies.     

Carbon Budget and Molecular Structure of Natural Organic Matter in Bank Infiltrated Groundwater

Managed aquifer recharge (MAR) provides means to remove natural organic matter (NOM) from surface waters. Recent studies have explored the degree of NOM removal in groundwater. In this study, we further elaborate the NOM removal at a lakeside natural bank infiltration site that functions as a surrogate for MAR. Our objective was to quantify the carbon budget in the aquifer based on concentration measurements of dissolved (in)organic carbon, and the molecular changes in NOM using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). According to the carbon budget, only 25% of the dissolved carbon entering the aquifer was organic, and it predominantly originated from lake water. Of the inorganic majority, on average 40% was produced in the vadose zone above the groundwater table, 31% in the lake bank, 22% in the aquifer as a result of degrading organic matter of lake water, and 7% in the lake. Seasonal concentration variations suggested that the lake bank was the main carbon source in the summer, increasing the carbon concentration of infiltrating lake water, that is, 3.0 mg/L to 7.9 mg/L. FT-ICR MS results showed 4960 to 5330 individual compounds in lake and groundwater. NOM removal in the aquifer was selective: the relative abundance of oxygen-containing species decreased from 75 to 31%, while the relative abundance of sulfur-containing species increased from 15 to 57%. The average molecular weights of both species remained unchanged. The study highlighted the role of lake bank processes and sulfur-containing species in groundwater quality.     

The origin of enriched mantle beneath São Miguel, Azores

Lavas from the island of São Miguel, Azores Archipelago have long been known to display large radiogenic isotopic variability, that ranges from “depleted” isotopic signatures (e.g. high ε_Nd ∼ +5) in the west, typical of many ocean island basalts, to more “enriched” compositions (e.g. low ε_Nd ∼ +1) in the east. Here, we further characterise the geochemistry of lavas from this remarkable locality, focussing on the nature and origin of the enriched source. Our new isotope data define a striking, linear array in Nd and Hf isotope space that points towards an unusual, enriched composition below the mantle array. This distinctive Hf-Nd isotope signature is associated with elevated values of all three radiogenic Pb isotope ratios. Although the enriched component has certain geochemical similarities to both terrigenous sediments and some samples of the continental mantle lithosphere, such comparisons do not stand closer examination. In the absence of a clear, modern analogue we explore the isotope evolution of some simple, model melt compositions to investigate plausible means of producing an appropriate enriched component. Nd-Hf isotope characteristics provide the tightest constraints and can be reproduced by an ancient (∼3 Ga), modest-degree melt (∼2%) from a garnet peridotite source. Currently, modest-degree melts from garnet-bearing sources are found forming some major oceanic islands. Subduction, isolation and later mixing of small amounts (<5%) of such basaltic material with more ubiquitous ambient mantle can account for the isotopic characteristics of the enriched São Miguel source. Yet the incompatible element ratios of the enriched São Miguel lavas do not show “recycled” signatures of near-surface alteration nor subduction zone dehydration. Thus, we infer that the enriched component was originally under-plated basalt, intruded into oceanic mantle lithosphere rather than forming the island edifice itself. Since the extreme isotope compositions of São Miguel reflect unextraordinary, albeit ancient, magmatic fractionation, the general rarity of such signatures indicates the efficiency of mantle processes in homogenising or hiding similar sources.     

Constraints on source-forming processes of West Greenland kimberlites inferred from Hf-Nd isotope systematics

Kimberlites from West Greenland have Hf-Nd isotope as well as major and trace element compositions that are similar to other Group I kimberlites, but that are distinctive in the spectrum of magmas sampled at Earth’s surface. The West Greenland kimberlites have ε_Ndi that ranges from +1.6 to +3.1 and ε_Hfi that ranges from −4.3 to +4.9. The samples exhibit ubiquitous negative Δε_Hfi (deviation from the ocean island basalt ε_Hf-ε_Nd reference line), ranging from −1.8 to −11.2. The kimberlites are characterized by steep heavy rare earth element patterns, positive Ta-Nb anomalies and negative Hf-Zr anomalies. These chemical signals are consistent with the presence of ancient, subducted oceanic crust in the kimberlite source region. In the model we present, dewatering and possibly partial melting of rutile-bearing oceanic crust during subduction results in characteristic trace element patterns in the residual crust. During aging, the Hf-Nd isotopic composition of this dewatered/partially melted EMORB-type crust evolves to negative Δε_Hfi values. Metasomatic fluids derived from this ancient subducted oceanic crust infiltrate and impart their trace element and isotopic signal on proximal peridotitic mantle. Melting of this metasomatized mantle peridotite results in kimberlite magmas.     

Seasonal food web structures and sympagic-pelagic coupling in the European Arctic revealed by stable isotopes and a two-source food web model

We simultaneously followed stable carbon (δ¹³C) and nitrogen (δ¹⁵N) isotopes in a two-source food web model to determine trophic levels and the relative importance of open water- and ice-associated food sources (phytoplankton vs. ice algae) in the lower marine food web in the European Arctic during four seasons. The model is based upon extensive seasonal data from 1995 to 2001.Phytoplankton, represented by samples of particulate organic matter from open water (Pelagic-POM) and ice algae, represented by samples from the underside of the ice (Ice-POM), were isotopically different. Ice-POM was generally dominated by the typical ice diatoms Nitzschia frigida and Melosira arctica and was more enriched than Pelagic-POM in ¹³C (δ¹³C = −20‰ vs. −24‰), but less enriched in ¹⁵N (δ¹⁵N = 1.8‰ vs. 4.0‰). However, when dominated by pelagic algae, Ice-POM was enriched in ¹³C and ¹⁵N similarly to Pelagic-POM.The derived trophic enrichment factors for δ¹⁵N (Δ_N = 3.4‰) and δ¹³C (Δ_C = 0.6‰) were similar in both pelagic and sympagic (ice-associated) systems, although the Δ_C for the sympagic system was variable.Trophic level (TL) range for zooplankton (TL = 1.8-3.8) was similar to that of ice fauna (TL = 1.9-3.7), but ice amphipods were generally less enriched in δ¹⁵N than zooplankton, reflecting lower δ¹⁵N in Ice-POM compared to Pelagic-POM. For bulk zooplankton, TLs and carbon sources changed little seasonally, but the proportion of herbivores was higher during May-September than in October and March. Overall, we found that the primary carbon source for zooplankton was Pelagic-POM (mean 74%), but depending on species, season and TL, substantial carbon (up to 50%) was supplied from the sympagic system. For bulk ice fauna, no major changes were found in TLs or carbon sources from summer to autumn. The primary carbon source for ice fauna was Ice-POM (mean 67%), although ice fauna with TL > 3 (adult Onisimus nanseni and juvenile polar cod) primarily utilized a pelagic food source.     

Detection of Anthropogenic CO2 Emission Signatures with TanSat CO2 and with Copernicus Sentinel-5 Precursor (S5P) NO2 Measurements: First Results

China’s first carbon dioxide(CO₂) measurement satellite mission, TanSat, was launched in December 2016. This paper introduces the first attempt to detect anthropogenic CO₂ emission signatures using CO₂ observations from TanSat and NO₂ measurements from the TROPOspheric Monitoring Instrument(TROPOMI) onboard the Copernicus Sentinel-5 Precursor(S5P) satellite. We focus our analysis on two selected cases in Tangshan, China and Tokyo, Japan.We found that t...     

Physical and biological characteristics of the pelagic system across Fram Strait to Kongsfjorden

The Fram Strait is very important with regard to heat and mass exchange in the Arctic Ocean, and the large quantities of heat carried north by the West Spitsbergen Current (WSC) influence the climate in the Arctic region as a whole. A large volume of water and ice is transported through Fram Strait, with net water transport of 1.7–3.2 Sv southward in the East Greenland Current and a volume ice flux in the range of 0.06–0.11 Sv. The mean annual ice flux is about 866,000 km² yr⁻¹. The Kongsfjorden–Krossfjorden fjord system on the coast of Spitsbergen, or at the eastern extreme of Fram Strait, is mainly affected by the northbound transport of water in the WSC. Mixing processes on the shelf result in Transformed Atlantic Water in the fjords, and the advection of Atlantic water also carries boreal fauna into the fjords. The phytoplankton production is about 80 g C m⁻² yr⁻¹ in Fram Strait, and has been estimated both below and above this for Kongsfjorden. The zooplankton fauna is diverse, but dominated in terms of biomass by calanoid copepods, particularly Calanus glacialis and C. finmarchicus. Other important copepods include C. hyperboreus, Metridia longa and the smaller, more numerous Pseudocalanus (P. minutus and P. acuspes), Microcalanus (M. pusillus and M. pygmaeus) and Oithona similis. The most important species of other taxa appear to be the amphipods Themisto libellula and T. abyssorum, the euphausiids Thysanoessa inermis and T. longicaudata and the chaetognaths Sagitta elegans and Eukrohnia hamata. A comparison between the open ocean of Fram Strait and the restricted fjord system of Kongsfjorden–Krossfjorden can be made within limitations. The same species tend to dominate, but the Fram Strait zooplankton fauna differs by the presence of meso- and bathypelagic copepods. The seasonal and inter-annual variation in zooplankton is described for Kongsfjorden based on the record during July 1996–2002. The ice macrofauna is much less diverse, consisting of a handful of amphipod species and the polar cod. The ice-associated biomass transport of ice-amphipods was calculated, based on the ice area transport, at about 3.55 × 10⁶ ton wet weight per year or about 4.2 × 10⁵ t C yr⁻¹. This represents a large energy input to the Greenland Sea, but also a drain on the core population residing in the multi-year pack ice (MYI) in the Arctic Ocean. A continuous habitat loss of MYI due to climate warming will likely reduce dramatically the sympagic food source. The pelagic and sympagic food web structures were revealed by stable isotopes. The carbon sources of particulate organic matter (POM), being Ice-POM and Pelagic-POM, revealed different isotopic signals in the organisms of the food web, and also provided information about the sympagic–pelagic and pelagic–benthic couplings. The marine food web and energy pathways were further determined by fatty acid trophic markers, which to a large extent supported the stable isotope picture of the marine food web, although some discrepancies were noted, particularly with regard to predator–prey relationships of ctenophores and pteropods.     

A hafnium isotope and trace element perspective on melting of the depleted mantle

New Hf isotope and trace element data on mid-ocean ridge basalts (MORB) from the Pacific Ocean basin are remarkably uniform (¹⁷⁶Hf/¹⁷⁷Hf≈0.28313–0.28326) and comparable to previously published data [Salters, Earth Planet. Sci. Lett. 141 (1996) 109–123; Patchett, Lithos 16 (1983) 47–51]. Atlantic MORB have ¹⁷⁶Hf/¹⁷⁷Hf ranging from 0.28302 to 0.28335 confirming the wide range originally identified by Patchett and Tatsumoto [Geophys. Res. Lett. 7 (1980) 1077–1080]. Indian MORB define an even wider range, from 0.28277 to 0.28337, but three exotic samples have very unradiogenic Hf isotope compositions. Their very low ¹⁷⁶Hf/¹⁷⁷Hf ratios, together with their trace element characteristics, require the presence of unusual plume-type material beneath the Indian ridge. All other Indian MORB have uniform Hf isotope compositions at about 0.2832, and define a small field displaced to the right of other MORB in Hf–Nd isotope space. The distinct nature of Indian MORB is best explained by the presence in Indian depleted mantle of old recycled oceanic crust and pelagic sediments. Sm/Hf ratios calculated from new high-precision rare earth element and Hf trace element data do not vary in MORB in the same way as in ocean island basalts (OIB): ratios are constant in OIB, but decrease with increasing Sm contents in MORB. The constancy of Sm/Hf in OIB is probably due to an overwhelming influence of residual garnet during melting. By contrast, the decrease of Sm/Hf in MORB is due to the effect of clinopyroxene in the residue of melting beneath ridges, an interpretation confirmed by quantitative modeling of melting. The relationship between Sm/Nd and Lu/Hf ratios in MORB does not require the presence of garnet in the residual mineralogy. The decoupling of Lu/Hf ratios and Hf isotope compositions – the so-called Hf paradox [Salters and Hart, EOS Trans. Am. Geophys. Union 70 (1989) 510] – can be explained by melting dominantly in the spinel field at shallow depths beneath mid-ocean ridges.     

Nd–Sr–Hf–O isotope provinciality in the northernmost Arabian–Nubian Shield: implications for crustal evolution

Multi-isotope study including whole-rock Nd–Sr, single zircon Hf, and SIMS δ¹⁸O analyses of zircons sheds light on magma sources in the northernmost Arabian–Nubian Shield (ANS) during ~820–570 Ma. Reconnaissance initial Nd and Sr isotope data for the older rocks (~820–740 Ma) reaffirms previous estimates that early crustal evolution in this part of the shield involved some crustal contamination by pre-ANS material. Prominent isotope provinciality is displayed by post-collisional calc-alkaline and alkaline igneous rocks of ~635–570 Ma across a NW-SE transect across basement of the Sinai Peninsula (Egypt) and southern Israel. Silicic rocks of the NW-region are characterized by lower εNd(T)–εHf(T) and higher Sr_i and δ¹⁸O compared with rocks of the SE-region, and the transition between the regions is gradual. Within each region isotope ratios are independent of the extent of magma fractionation, and zircon cores and rims yield similar δ¹⁸O values. Comparison with southern segments of the ANS shows that the source for most ~635–570 Ma rocks can be modeled as the isotopically aged lower-intermediate crust in the ANS core (SE-region) and its northern, more contaminated ANS margins (NW-region). Nevertheless, Nd–Sr isotope enrichment of the lithospheric mantle is indicated by some basic magmas of the NW-region displaying the most enriched Nd–Sr isotope compositions. Comparison of Nd and Hf depleted mantle model ages for rocks of the SE-region may indicate that crustal formation events in the ANS geographical core took place at 1.1–1.2 Ga and were followed by crustal differentiation starting at ~0.9 Ga.