Characterisation of a Natural Quartz Crystal as a Reference Material for Microanalytical Determination of Ti, Al, Li, Fe, Mn, Ga and Ge

A natural smoky quartz crystal from Shandong province, China, was characterised by laser ablation ICP-MS, electron probe microanalysis (EPMA) and solution ICP-MS to determine the concentration of twenty-four trace and ultra trace elements. Our main focus was on Ti quantification because of the increased use of this element for titanium in- quartz (TitaniQ) thermobarometry. Pieces of a uniform growth zone of 9 mm thickness within the quartz crystal were analysed in four different LA-ICP-MS laboratories, three EPMA laboratories and one solution-ICP-MS laboratory. The results reveal reproducible concentrations of Ti (57 ± 4 lg g-1),Al (154 ± 15 lg g-1), Li (30 ± 2 lg g-1), Fe (2.2 ± 0.3 lg g-1), Mn (0.34 ± 0.04 lg g-1), Ge (1.7 ± 0.2 lg g-1) and Ga (0.020 ± 0.002 lg g-1) and detectable, but less reproducible, concentrations of Be, B, Na, Cu, Zr, Sn and Pb. oncentrations of K, Ca, Sr, Mo, Ag, Sb, Ba and Au were below the limits of detection of all three techniques. The uncertainties on the average concentration determinations by multiple techniques and laboratories for Ti, Al, Li, Fe, Mn, Ga and Ge are low; hence, this quartz can serve as a reference material or a secondary reference material for microanalytical applications involving the quantification of trace elements in quartz.

Superspace description of wagnerite-group minerals (Mg,Fe,Mn) 2 (PO 4 )(F,OH)

Reinvestigation of more than 40 samples of minerals belonging to the wagnerite group (Mg, Fe, Mn)2(PO4)(F,OH) from diverse geological environments worldwide, using single-crystal X-ray diffraction analysis, showed that most crystals have incommensurate structures and, as such, are not adequately described with known polytype models (2b), (3b), (5b), (7b) and (9b). Therefore, we present here a unified superspace model for the structural description of periodically and aperiodically modulated wagnerite with the (3+1)-dimensional superspace group C2/c(0[beta]0)s0 based on the average triplite structure with cell parameters a [asymptotically equal to] 12.8, b [asymptotically equal to] 6.4, c [asymptotically equal to] 9.6 Å, [beta] [asymptotically equal to] 117° and the modulation vectors q = [beta]b*. The superspace approach provides a way of simple modelling of the positional and occupational modulation of Mg/Fe and F/OH in wagnerite. This allows direct comparison of crystal properties.

Proposal for an International Molybdenum Isotope Measurement Standard and Data Representation

Molybdenum isotopes are increasingly widely applied in Earth Sciences. They are primarily used to investigate the oxygenation of Earth's ocean and atmosphere. However, more and more fields of application are being developed, such as magmatic and hydrothermal processes, planetary sciences or the tracking of environmental pollution. Here, we present a proposal for a unifying presentation of Mo isotope ratios in the studies of mass-dependent isotope fractionation. We suggest that the δ98/95Mo of the NIST SRM 3134 be defined as +0.25‰. The rationale is that the vast majority of published data are presented relative to reference materials that are similar, but not identical, and that are all slightly lighter than NIST SRM 3134. Our proposed data presentation allows a direct first-order comparison of almost all old data with future work while referring to an international measurement standard. In particular, canonical δ98/95Mo values such as +2.3‰ for seawater and −0.7‰ for marine Fe–Mn precipitates can be kept for discussion. As recent publications show that the ocean molybdenum isotope signature is homogeneous, the IAPSO ocean water standard or any other open ocean water sample is suggested as a secondary measurement standard, with a defined δ98/95Mo value of +2.34 ± 0.10‰ (2s). Les isotopes du molybdène (Mo) sont de plus en plus largement utilisés dans les sciences de la Terre. Ils sont principalement utilisés pour étudier l'oxygénation de l'océan et de l'atmosphère de la Terre. Cependant, de plus en plus de domaines d'application sont en cours de développement, tels que ceux concernant les processus magmatiques et hydrothermaux, les sciences planétaires ou encore le suivi de la pollution environnementale. Ici, nous présentons une proposition de présentation unifiée des rapports isotopiques du Mo dans les études du fractionnement isotopique dépendant de la masse. Nous suggérons que le δ98/95Mo du NIST SRM 3134 soit définit comme étant égal à +0.25 ‰. La raison est que la grande majorité des données publiées sont présentés par rapport à des matériaux de référence qui sont similaires, mais pas identiques, et qui sont tous légèrement plus léger que le NIST SRM 3134. Notre proposition de présentation des données permet une comparaison directe au premier ordre de presque toutes les anciennes données avec les travaux futurs en se référant à un standard international. En particulier, les valeurs canoniques du δ98/95Mo comme celle de +2,3 ‰ pour l'eau de mer et de -0,7 ‰ pour les précipités de Fe-Mn marins peuvent être conservés pour la discussion. Comme les publications récentes montrent que la signature isotopique moyenne du molybdène de l'océan est homogène, le standard de l'eau océanique IAPSO ou tout autre échantillon d'eau provenant de l'océan ouvert sont proposé comme standards secondaires, avec une valeur définie du δ98/95 Mo de 2.34 ± 0.10 ‰ (2s).

Polycyclic aromatic compounds (PAHs and oxygenated PAHs) and trace metals in fish species from Ghana (West Africa): Bioaccumulation and health risk assessment

We report the concentrations of 28 PAHs, 15 oxygenated PAHs (OPAHs) and 11 trace metals/metalloids (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, and Zn) in muscle and gut + gill tissues of demersal fishes (Drapane africana, Cynoglossus senegalensis and Pomadasys peroteti) from three locations along the coast of the Gulf of Guinea (Ghana). The concentrations of ∑ 28PAHs in muscle tissues averaged 192 ng g− 1 dw (range: 71–481 ng g− 1 dw) and were not statistically different between locations. The concentrations of ∑ 28 PAHs were higher in guts + gills than in muscles. The PAH composition pattern was dominated by low molecular weight compounds (naphthalene, alkyl-naphthalenes and phenanthrene). All fish tissues had benzo[a]pyrene concentrations lower than the EU limit for food safety. Excess cancer risk from consumption of some fish was higher than the guideline value of 1 × 10− 6. The concentrations of ∑ 15 OPAHs in fish muscles averaged 422 ng g− 1 dw (range: 28–1715 ng g− 1dw). The ∑ 15 OPAHs/∑ 16 US-EPA PAHs concentration ratio was > 1 in 68% of the fish muscles and 100% of guts + gills. The log-transformed concentrations of PAHs and OPAHs in muscles, guts + gills were significantly (p < 0.05) correlated with their octanol–water partitioning coefficients, strongly suggesting that equilibrium partitioning from water/sediment into fish tissue was the main mechanism of bioaccumulation. The trace metal concentrations in the fish tissues were in the medium range when compared to fish from other parts of the world. The concentrations of some trace metals (Cd, Cu, Fe, Mn, Zn) were higher in guts + gills than in muscle tissues. The target hazard quotients for metals were < 1 and did not indicate a danger to the local population. We conclude that the health risk arising from the consumption of the studied fish (due to their PAHs and trace metals content) is minimal.

Influence of the Central American Seaway and Drake Passage on ocean circulation and neodymium isotopes: A model study

The sensitivity of the neodymium isotopic composition (ϵNd) to tectonic rearrangements of seaways is investigated using an Earth System Model of Intermediate Complexity. The shoaling and closure of the Central American Seaway (CAS) is simulated, as well as the opening and deepening of Drake Passage (DP). Multiple series of equilibrium simulations with various intermediate depths are performed for both seaways, providing insight into ϵNd and circulation responses to progressive throughflow evolutions. Furthermore, the sensitivity of these responses to the Atlantic Meridional Overturning Circulation (AMOC) and the neodymium boundary source is examined. Modeled ϵNd changes are compared to sediment core and ferromanganese (Fe-Mn) crust data. The model results indicate that the North Atlantic ϵNd response to the CAS shoaling is highly dependent on the AMOC state, i.e., on the AMOC strength before the shoaling to shallow depths (preclosure). Three scenarios based on different AMOC forcings are discussed, of which the model-data agreement favors a shallow preclosure (Miocene) AMOC (∼6 Sv). The DP opening causes a rather complex circulation response, resulting in an initial South Atlantic ϵNd decrease preceding a larger increase. This feature may be specific to our model setup, which induces a vigorous CAS throughflow that is strongly anticorrelated to the DP throughflow. In freshwater experiments following the DP deepening, ODP Site 1090 is mainly influenced by AMOC and DP throughflow changes, while ODP Site 689 is more strongly influenced by Southern Ocean Meridional Overturning Circulation and CAS throughflow changes. The boundary source uncertainty is largest for shallow seaways and at shallow sites.