Laser Ablation Inductively Coupled Plasma Mass Spectrometry Research Articles

The role of silver nanoparticles effects in the homeostasis of metals in soybean cultivation through qualitative and quantitative laser ablation bioimaging

BackgroundNanoparticles (NPs) are currently found in the world in the form of natural colloids and volcanic ash, as well as in anthropogenic sources, such as nanofertilizers; however, in the literature, there is still a lack of toxicological evidence, risk assessment, and regulations about the use and environmental impact of NPs in the agroindustrial system. Therefore, the aim of this work was to evaluate alterations caused by the presence of AgNPs during the development of soybean plants. MethodsThe BRS232 non-transgenic (NT) soybean plant and 8473RR (TRR) and INTACTA RR2 PRO (TIntacta) transgenic soybean plants were irrigated for 18 days under controlled conditions with deionized water (control), AgNPs, and AgNO3. The isotopes 107Ag+, 55Mn+, 57Fe+, 63Cu+, and 64Zn+ were mapped in leaves, using 13C+ as an internal standard (IS), and carried out using a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) technique with a Nd:YAG (213 nm) laser source in the imagagin mode using the LA-iMageS software and also Mathlab. ResultsLeaf images showed a low Ag translocation, indicated by the basal signal of this ion. Additionally, the presence of Ag in the ionic form and as NPs altered the homeostasis of 112Cd+, 64Zn+, 55Mn+, 63Cu+, and 57Fe+ in different ways. Quantitative image analysis was performed for Cu. ConclusionThe behavior of TRR and TIntacta plants was different in the presence of ionic silver or AgNPs, confirming that the metabolism of these two plants, despite both being transgenic, are different. Through the images, it was observed that the response of plants was different in the face of the same stress conditions during their development.

Improving the chronostratigraphic framework of the Transvaal Supergroup (South Africa) through in-situ and high-precision U-Pb geochronology

The Transvaal Supergroup, on the Kaapvaal Craton in South Africa, is widely accepted as one of the best-preserved sedimentary archives to constrain planetary-scale environmental changes during the late Archean and early Proterozoic, yet the sedimentation age for certain stratigraphic intervals remains poorly constrained. To improve the temporal control on some of the first-order global changes recorded in these rocks, we carried out U-Pb analyses of detrital zircon populations from several clastic and volcano-clastic sedimentary units of the Transvaal Supergroup. We applied the Chemical Abrasion-Isotope Dilution-Thermal Ionization Mass Spectrometry (CA-ID-TIMS) technique on detrital and volcanic zircon populations that had been previously screened using the Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) technique. We report new maximum depositional age estimates for the Pannetjie (2456.6 ± 7.0 Ma), the Heynskop (2451.5 ± 2.5 Ma), the Makganyene (2423.1 ± 1.0 Ma) and the Hekpoort formations (2248.0 ± 1.1 Ma).A ca. 2.25 Ga-old cluster of LA-ICP-MS analyses in the Makganyene Formation was identified to be spurious, since it was completely removed during the chemical abrasion. Thus, we speculate that circulation of hydrothermal fluids and associated Pb-loss from a radiation-damaged lattice during the emplacement of the much younger Hekpoort Formation or possibly the Ophthalmia Orogeny, recorded in Western Australia, may have reset the U-Pb system of this zircon population. This implies that the accurate maximum depositional age of the Makganyene Formation is ca. 2.42 Ga instead, which denotes the age of the oldest glacial event of global extent during the Paleoproterozoic. Therefore, we suggest that the combination of both dating techniques is essential to ensure accurate maximum depositional age constraints for ancient detrital sedimentary rocks. Additionally, our data provides temporal constraints on a period characterized by major fluctuations in atmospheric oxygen. Finally, and supporting the complex nature of the Paleoproterozoic, linkages between widespread glaciations and atmospheric oxygen fluctuations remain to be explored.

Exploring the link between spatiotemporal patterns of plutonism and geodynamic regimes at the end of Archean: an example from the northeastern Superior Province, Canada

This paper presents new U–Pb zircon ages obtained using laser ablation ICP-MS from various plutonic units that intruded along the southern margin of the Bienville domain, a presumed Neoarchean magmatic arc in the northeastern Superior Province, Québec, Canada. The U–Pb ages indicate that the arc plutons were emplaced episodically between ca. 2745 Ma and ca. 2697 Ma, synchronous with regional transpressional deformation. Furthermore, the observed intra-pluton age variations show that the largest examined intrusion, the Radisson pluton, grew incrementally over a period of at least 15 My, perhaps in a series of elongated, sheet-like magma batches straddling the presumed arc margin and emplaced successively, younging inwards. This emplacement style is comparable (though not unique) to modern arc plutons emplaced along or within regional transpressional shear zones. The new ages are then complemented with a statistical analysis of previously published U–Pb pluton zircon ages from the adjacent units (La Grande, Opinaca, Opatica), which revealed a subtle southward-younging trend (i.e., towards the presumed trench) in otherwise broadly coeval and areally extensive plutonism characterized by diverse compositions. The observed spatiotemporal pattern of plutonism is transitional between unfocused, plume-related magmatic centers and focused, unidirectionally migrating magmatism of modern arcs, perhaps as a result of hotter environment and complex interplay between the waning plume-related regime and increasingly dominating modern-style plate tectonics at the end of Archean.

Indigenous labor and the circulation of majolica in the colonial Andes

This study examines compositional data from Laser-Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) analysis of eighty-four samples of tin enameled ware (majolica) recovered from Spanish colonial period contexts of two regions (north coast and south-central highlands) in the Peruvian Andes. We identify four compositional groups and discuss their distribution as evidence of the circulation of majolica in the Colonial Andes, with particular attention to the roles that Indigenous people played in their transport and use. While most of these materials appear to have been produced at Panama la Vieja, the presence of three additional groups of likely Peruvian origin suggests a more complex network of production and exchange that points to the diverse ways in which Indigenous labor structured colonial economic networks.

Crystal chemistry of ferriallanite-(Ce) from Nya Bastnäs, Sweden: Chemical and spectroscopic study

A second study of ferriallanite-(Ce) from Nya Bastnäs, Sweden, extends current data by using electron probe micro-analysis (EPMA), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis and brings new insights about its crystal chemistry obtained by Raman spectroscopy. The study presents the first Raman spectra for ferriallanite-(Ce) member of the allanite group (not considering the rather low-quality spectra published in preceding papers). The material does not show significant radiation damage, which is rare as allanite-group minerals often have undergone metamictisation due to significant amounts of incorporated radionuclides (U, Th). Some interior regions show pronounced zoning that correlates with variations in Raman-band positions. In spite of its significant REE content, the material is virtually non-luminescent. New additional data for allanite-(Ce) from Oßling, Germany and Domanínek, Czech Republic are also presented, which were used for comparison.

Metasomatized mantle under the Eastern Mexican Alkaline Province: evidence from the Oligocene Rincón Murillo Gabbro, Sierra de San Carlos-Cruillas, NE México

The Cenozoic Sierra de San Carlos-Cruillas (SSCC) magmatic complex belongs to the Eastern Mexican Alkaline Province (EMAP). The SSCC mainly consists of plutonic and subvolcanic bodies displaying diverse lithological compositions. These rocks exhibit both OIB- and arc-like geochemical characteristics. In this contribution, we present new petrographic, geochemical, isotopic, and geochronological data of the Rincón Murillo Gabbro (RMG), situated in the southern part of the SSCC. The RMG is nepheline normative and displays an OIB-like intraplate character. Laser ablation ICP-MS U-Pb analyses on titanites yielded Oligocene (Rupelian) crystallization ages of 31.8 ± 1.8 and 31.0 ± 1.7 Ma. The 87Sr/86Sr(i) (0.703400–0.704159) and 143Nd/144Nd(i) (0.512732–0.512815) ratios indicate a mantle origin. Trace element data indicate the participation of different enriched mantle components in the source. One component is related to previous subduction processes, generating the HFSE-depleted arc-like magmas of San José Gabbro in the northern part of SSCC. The second component is related to deep mantle melts with a slightly carbonatitic signal and HFSE-enriched fluids derived from the subducted Hess conjugate plateau generating different enriched sources in the upper mantle under the SSCC. The passage, eclogitization, detachment and foundering of the Hess plateau gave rise to an asthenospheric upwelling that triggered the low to moderate partial melting degrees (3–15%) of an amphibole-bearing garnet peridotite, generating the OIB-like parental magmas of RMG, located in the southern part of SSCC. Two-component mixing, and AFC models indicate that variable degrees of crystal fractionation and minor crustal assimilation are involved in the evolution of Rincón Murillo Gabbro.

Mineralogy and Distribution of REE in Oxidised Ores of the Mount Weld Laterite Deposit, Western Australia

The Mount Weld rare earth element (REE) deposit, Western Australia, is one of the largest of its type on Earth. Current mining exploits the high-grade weathered goethite-bearing resource that lies above, and which represents the weathering product of a subjacent carbonatite. The mineralogy, petrography, deportment of lanthanides among the different components, and variation in mineral speciation, textures, and chemistry are examined. Microanalysis, involving scanning electron microscope (SEM) imaging, electron probe microanalysis (EPMA) and laser ablation inductively coupled-plasma mass spectrometry (LA-ICP-MS), was conducted on sized fractions of three crushed and ground laterite ore samples from current and planned production, and a representative sample from the underlying carbonatite. High-magnification imaging of particles in laterite samples show that individual REE-bearing phases are fine-grained and extend in size well below the micron-scale. Nanoscale inclusions of REE-phosphates are observed in apatite, Fe-(Mn)-(hydr)oxides, and quartz, among others. These have the appearance, particularly in fluorapatite, of pervasive, ultrafine dusty domains. Apart from the discrete REE minerals and abundant nano- to micron-scale inclusions in gangue, all ore components analysed by LA-ICP-MS contain trace to minor levels of REEs within their structures. This includes apatite, where low levels of REE are confirmed in preserved igneous apatite, but also Fe- and Mn-(hydr)oxides in which concentrations of hundreds, even thousands of ppm are measured. This is significant given that Fe-(Mn)-(hydr)oxides are the most abundant component of the laterite and points to extensive mobility and redistribution of REEs, and especially HREE, during progressive lateritisation. Late-formed minerals, notably tiny grains of cerianite, reflect a shift to oxidising conditions. REE-fluorocarbonates are the main host for REEs in carbonatite and are systematically replaced by hydrated, Ca-bearing REE-phosphates (largely rhabdophane). The latter displays varied compositions but is characteristically enriched in HREE relative to monazite in the same sample. Fine-grained, compositionally heterogeneous rhabdophane is accompanied by minor amounts of other paragenetically late, hydrated phosphates with enhanced MREE/HREE relative to LREE (although still LREE-dominant). Minor, relict xenotime and zircon are significant HREE carriers. Ilmenite and pyrochlore group members contain REE but contribute only negligibly to the overall REE budget. Although the proportions of individual mineral species differ, the chemistry of key ore components are similar in different laterite samples from the current resource. Mineral signatures are, however, subtly different in the lower grade southeastern part of the deposit, including higher concentrations of HREE relative to LREE in monazite, rhabdophane, florencite and Fe-(Mn)-(hydr)oxides.

Obsidian exchange networks and highland-lowland interaction in the Lesser Caucasus borderlands

Obsidian sourcing studies have a long history in the Near East, but relatively few have focused on obsidian exchange after the Early Bronze Age. Here, we present a multi-technique analysis of an assemblage of 111 obsidian artifacts from excavated Late Bronze and Early Iron Age (LBA-EIA; c. 15th-6th c BCE) contexts at Mtsvane Gora, southern Georgia. Because the site is situated in the lowland Kura Valley and the nearest obsidian sources are in the highlands to the south and west, obsidian provenance can serve as a proxy for mapping highland-lowland interactions. Chemical compositions analyzed via portable X-ray fluorescence spectrometry (pXRF), electron microprobe analysis (EMPA), and laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS), were compared with existing geological datasets of chemical analyses to identify the source of all but one of the artifacts analyzed. The results show that Chikiani, a source in the highlands of southern Georgia, was the geological origin of >90% of the objects analyzed. While acknowledging that obsidian exchange is just one aspect of highland-lowland interaction, this finding implies that Mtsvane Gora’s connections with the adjacent highlands were skewed towards greater engagement with some highland areas relative to others. More generally, the research suggests that geographic adjacency of highlands and lowlands does not necessarily mean that they were highly interconnected.

LA-ICP-MS analyses of trace elements in zoned sphalerite: A study from the Maoping carbonate-hosted Pb-Zn(-Ge) deposit, southwest China

In southwest China, many Pb-Zn deposits are described as low temperature carbonate-hosted deposits or Mississippi Valley-type (MVT) deposits. But trace element distribution and concentration in sphalerite between deposits may significantly vary and could possibly imply alternative deposit-types. An investigation was carried out on sphalerite (Sp-II) in the main ore stage of the Maoping carbonate-hosted Pb-Zn(-Ge) deposit (Southwest China), based on laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Here, Sp-II is divided into the dark red, yellow–brown, and light-yellow zones. Principal component analysis revealed element clusters distributed within distinct zoning types in Sp-II: the dark red zones are enriched in Mn, Fe, and Cd; the yellow–brown zones are enriched in Cu, Ge, Ag, and Sb; the light-yellow zones are enriched in Ga. Trace elements in Sp-II record temperature and sulfur fugacity (fS2) evolution of ore-forming fluid system, which tends to decrease from the dark red to yellow–brown to light-yellow zones. The formation of Sp-II may be an external process resulting from the varieties of temperature and fS2 in the ore-forming fluid, which may be driven by rock buffer. Here, Manganese, Fe, and Cd are preferentially incorporated in the relatively higher temperatures and fS2, whereas Ga is preferentially incorporated in the relatively lower those. Regardless of the zoning type, strong binary correlations between Ge and Cu as well as the high similarity of their concentration distribution in mapping images suggest coupled substitutions as Ge4+ + 2Cu+ ↔ 3Zn2+ and/or Ge2+ + 2Cu+ ↔ 2Zn2+ + vacancy. A trace element comparison of various Pb-Zn deposits in the world, including our new data from Maoping shows a distinctive signature for the Maoping deposit. Homogenization temperatures (217–430 ℃, mean 298 ℃) of the newly discovered ore body (No. VI) support that Maoping is a medium–high temperature carbonate-hosted deposit.

Ultraviolet-photoluminescence and trace element analyses in Ga-rich sphalerite from the Djebel Gustar Zn-Pb deposit, Algeria

The Djebel Gustar Zn-Pb deposit in northeastern Algeria is one of many carbonate-hosted base metal deposits in the Atlas metallogenic province of North Africa. The sphalerite in this deposit occurs in five distinct types that differ in texture, mineral assemblage, chemical composition, and UV photoluminescence signature. Detailed investigation of trace elements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) showed that the sphalerite is significantly enriched in the critical metal Ga. The trace element concentrations of the different sphalerite types correlated well with their photoluminescence color; with Mn2+ (orange-yellow), Cu+ (green), and Ga3+ (red) being the dominant activators. We suggest that the Ga enrichment in the Djebel Gustar deposit is the result of formation conditions that include the mixing of a Cl-rich fluid carrying mainly Zn and Pb with a more reduced and Cl-poor fluid containing considerable organic matter and/or calcite with adsorbed Ga(OH)3. This Ga was subsequently incorporated into sphalerite, rather than forming a stoichiometric Ga phase. Furthermore, our study demonstrates that UV photoluminescence of low Fe sphalerite has the potential to become a simple and affordable tool for preliminary characterization of sphalerite ores in mining and exploration with respect to critical elements such as Ga.

Luminescence Characteristics of Green Grossular Garnets

Some light green grossular garnets exhibit orange-red luminescence under long-wave and short-wave ultraviolet light. To characterize their luminescence behavior, we studied seven grossular garnets with typical colors ranging from light yellowish-green to intense green by using photoluminescence (PL), ultraviolet–visible (UV–Vis) spectroscopy, electron paramagnetic resonance (EPR), Electron Probe Microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). In the PL spectra of these grossular garnets samples, a broad band exists at about 589 nm and three sharp peaks appear at 697, 702 and 716 nm. The three-dimensional fluorescence spectra reveal two luminescence emissions. They are (1) a broad band near 600 nm; and (2) a series of sharp peaks centered at 697, 702 and 716 nm. In the UV–Vis spectra, two prominent asymmetrical absorption bands near 430 and 605 nm are related to Cr3+ or Cr3+/V3+, and minor absorption peaks at 408 and 419/420 nm are related to Mn2+. EMPA and LA-ICP-MS analysis confirmed the existence of trace elements Ti, V, Cr and Mn. Furthermore, the EPR spectrum excluded the existence of V2+ and V4+ and confirmed the existence of Mn2+, Cr3+ and Fe3+. Regarding V, an interesting phenomenon was reported in which the intensity of luminescence could be suppressed in grossular garnets with higher concentrations of V. These results imply that chromium and manganese are the luminescence activators in grossular garnets, and vanadium is a powerful quencher.

Early Precambrian mafic dykes in western Shandong province, North China Craton: constraints on the chronology, genetic model and tectonic significance

AbstractIn the Late Neoarchaean, the lithosphere of the North China Craton (NCC) experienced a strong extensional event, which is of great significance for understanding the evolution of the continental crust in the Precambrian. In this study, a suite of mafic dykes from Shandong province in the northeastern NCC were investigated to determine the nature, timing and source of rift-related magma activities using zircon U–Pb data, whole-rock geochemistry and Nd–Hf isotopes. Zircon U–Pb dating of four dolerites by laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) yielded weighted mean 207Pb/206Pb ages in the range 2509 ± 6.1 to 2537 ± 6.2 Ma (2σ, 95 % confidence interval). The mafic dykes are classified as alkaline rocks based on their K2O + Na2O contents (6.78–7.21 wt %) and belong to the shoshonitic series according to their K2O contents (3.23–3.36 wt %). The dolerites show low concentrations of light rare earth elements ((La/Yb)N between 7.17 and 8.55), positive Eu anomalies (Eu/Eu* between 1.12 and 1.27), positive Ba, K, Pb, Sr, Eu, Dy and Lu anomalies, and depleted U, Nb, Pr, Ta, P, Nd and Ti anomalies. The dykes are characterized by low initial (87Sr/86Sr)i (∼0.6969), positive εNd(t) values (0.2–0.8) and εHf(t) values (0.5–8.6) and relatively old mean Nd and Hf model age (2.73 Ga). Collectively, the data suggest that the mafic dykes were derived from the partial melting (10–20 %) of an isotope-depleted garnet–lherzolite mantle source that was hybridized through interaction with subducted lower crustal material. The parental magmas of these dykes underwent a certain number of crustal contaminations during magma ascent. The mafic magmatism represented in the form of the dyke swarms is considered to be a response to widespread lithospheric extension which affected the NCC at c. 2.5 Ga during the Neoarchaean.

Trace elements of sulfides in the Dengjiashan Pb–Zn deposit from West Qinling, China: Implications for mineralization conditions and genesis

Dengjiashan is a large‐scale Pb–Zn deposit discovered in the western part of the Xicheng ore field within the West Qinling metallogenic belt. Information regarding the distribution and occurrence of trace elements in ore minerals and mineralization, as well as the genesis of this deposit, remains scarce. Laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) analysis and elemental mapping were used to determine the distribution and occurrence of trace elements in the sulfide minerals of the Dengjiashan deposit, as well as delineate the process of its genesis. Our results showed that the trace elements enriched in the different sulfides were significantly different. Sphalerite is the main carrier mineral of the scattered elements Cd, Ge and Ga. Based on the trace element content and ratio, principal component analysis and colour of the sphalerite and pyrite, the deposit likely formed in a medium‐temperature environment. The comparative analysis of trace elements from multiple deposits of different origins, combined with the geological characteristics and distribution of sulfide trace elements, suggests that Dengjiashan is a sedimentary exhalative (SEDEX)‐type deposit. As the metallogenic process had a closer relationship to medium‐low temperature hot brine and later tectonic metamorphic hydrothermal fluid, than with magmatic hydrothermal fluid, the deposit is likely of non‐magmatic SEDEX–hot brine superimposed transition origin. This study provides additional insight on the distribution of trace elements in the sulfide minerals of the Dengjiashan deposit, as well as the processes that led to its formation, and may further facilitate ongoing and future key metal prospecting and exploration efforts.

Impact of Wood Ash and Sewage Sludge on Elemental Content in Hybrid Alder Clone

In this study, the focus was on evaluating the effects of the initial treatment of wood ash and sewage sludge on hybrid alder clones’ aboveground biomass and elemental content. To measure the element concentrations in the tree rings, laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) was utilized, which is a valuable tool for dendrochemistry research, albeit with some challenges in accurate quantification. One important aspect of the study was the development and comparison of different “in-house” matrix-matched standards for the precise quantification of element concentrations in tree rings. It was found that the commercially available reference materials, IAEA 413 (algae) and IAEA 392 (algae), were the best choices due to their homogeneity. The study also revealed that the use of sewage sludge and wood ash as soil improvers significantly benefited the increase in hybrid alder biomass. However, no significant increase in element content was found in the obtained wood mass, and for some elements, there was a decrease in concentration.

Disordered dolomite as an unusual biomineralization product found in the center of a natural Cassis pearl.

Natural pearls are produced without human intervention, mainly due to various irritations from the surrounding environment to their mantle tissues. Pearls usually possess similar mineral compositions to the host shells, which means they are also dominated by aragonite and calcite. In this study, we report a natural pearl from a Cassis species mollusk containing granular central structures. Raman spectroscopy, laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), energy dispersive X-ray spectroscopy (EDS) coupled with scanning electron microscope (SEM), and X-ray diffraction (XRD) analyses were carried out in order to characterize the mineral composition in the center region of this pearl. Our results showed that this pearl's center was made of mostly disordered dolomite (Ca0.53Mg0.47CO3) mixing with small amount of aragonite and high magnesium-calcite. To the best of our knowledge, this is the first time disordered dolomite was conclusively identified inside of a natural pearl and such information expanded our knowledge on internal growth structures and formation of natural pearls.

Precise U-Pb dating of incremental calcite slickenfiber growth: Evidence for far-field Eocene fold reactivation in Ireland

Abstract The Variscan orogen in southern Ireland and Britain is characterized by an intensely deformed, E-W–trending fold-and-thrust belt. Farther north in Ireland, the Carboniferous North Dublin Basin exhibits tight chevron folds and kinematically linked en echelon vein sets, along with bedding-parallel veins with slickenfibers. This deformation is assumed to be Variscan in age, despite lying 150 km north of the supposed Variscan “front.” The laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) U-Pb dating of these calcite veins undertaken for this study showed that relict Variscan U-Pb ages are very poorly preserved. Instead, late Eocene ages were obtained from many calcite veins, including fold hinge breccias and bedding-parallel slickenfiber veins associated with N-S shortening (flexural slip). Also, U-Pb ages from one bedding-parallel vein showed protracted flexural slip over ~5 m.y. during late Eocene times. Detection of the growth domains within this vein was facilitated by the imaging approach to LA-ICP-MS U-Pb dating adopted in this study, which can identify age-homogeneous domains by integrating spatial U-Pb isotopic information with maps of petrogenetically diagnostic major and trace elements. The late Eocene fold reactivation phase was hitherto undetected on the Irish mainland, but regional Cenozoic N-directed shortening has been documented in Mesozoic–Cenozoic sequences of the southern Irish Sea, Celtic Sea, southern England, and the Paris Basin. We attribute late Eocene fold reactivation to far-field, N-directed shortening associated with the Alpine/Pyrenean orogenies. It is likely that many Variscan or Caledonian folds, particularly in southern onshore Ireland, were reactivated during Eocene–Oligocene shortening, which has not been recognized to date because of the lack of post-Variscan markers (e.g., dikes, Mesozoic–Cenozoic cover sequences).

Intra‐ and interspecific variation in trace element concentrations in feathers of north European trans‐African migrants

The knowledge of migratory connectivity is important for understanding the potential drivers of populations and it is thus important for conservation implications. Migratory connectivity of species can be studied using exogenous, such as rings and transmitters, or endogenous markers, such as stable isotopes and trace elements. The use of trace elements has been much less frequently studied compared to stable isotopes. Trace elements can be studied from the feathers of birds and this does not necessarily require trapping of individuals. Here we studied the variation of 18 different trace elements in feathers of two long‐distance trans‐African migrants, willow warblers Phylloscopus trochilus and barn swallows Hirundo rustica, using body feathers of museum specimens of birds from Finnish breeding grounds. The trace elements were measured using laser‐ablation inductively‐coupled‐plasma mass‐spectrometry (LA‐ICP‐MS). We show that trace element concentrations were relatively stable along the rachis within the same feather except in Ni and S, which showed a quadratic pattern. In general, variation within feathers of the same individuals was smaller than in feathers between individuals for most elements. Furthermore, concentrations of 11 trace elements showed significantly higher concentrations in willow warbler feathers collected in spring than in autumn, moulted in African wintering grounds and European breeding grounds, respectively. Last, concentrations of seven trace elements were significantly higher in the spring feathers of willow warblers compared to barn swallows. This suggests that trace elements could be used to separate moulting grounds of the birds on the larger scale within the same species, but also sampling design should be carefully considered.

The utility of otolith-based methods for discriminating stock structure of the fishery important monacanthid, Nelusetta ayraud, over an intermediate scale

Connectivity and population structure of exploited fish species are critical to understand for effective assessment and management at appropriate spatial scales. We provide a first look at connectivity and population structure of a fishery-important monacanthid, Nelusetta ayraud, using otolith-based methods to compare among three locations (220–540 km apart) along the coast of New South Wales (NSW), Australia. Otolith elemental signatures sampled with laser-ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) revealed differences between two of the three locations during a recent period before capture, as well as differences between the two times examined, although spatial differences were consistent across these times. In contrast, elemental signatures in the juvenile core of the otolith did not differ among locations. Sr:Ca increased linearly with age, and Ba:Ca initially increased to age 1+ before declining in older age classes, consistent with previous observations of an ontogenetic movement into deeper offshore waters for N. ayraud. No differences in otolith shape were detected among locations using Elliptical Fourier Analysis. Our findings suggest there may be spatial structuring of the N. ayraud stock over an intermediate scale (100s km) within NSW, which will inform the design of a larger nation-wide investigation.

Late beryllium enrichment during dynamic growth of vesuvianite and scapolite from the Cuonadong Sn-W-Be skarn, Tibet

The genesis of beryllium (Be) mineralization associated with granitic tin (Sn)- tungsten (W) deposit has received little attention, especially the fluid Be concentration variation along with the developing of skarn. For revealing the less-known skarn Be enrichment characteristics, in-situ electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) along with element mapping were performed on the Be-bearing vesuvianite and scapolite grains from the Cuonadong Sn-W-Be skarn. As the main Be-bearing calc-silicate minerals, the vesuvianite (X19Y13Z18T0-5O68W10) and scapolite (M4T12O24A) incorporate Be element via occupying normally vacant T site and the Al-2(SiBe) substitution, respectively, and show outward increased Be content related to the varying solid-solution composition arising from the dynamic evolution of skarn. The homogeneous core enveloped by oscillatory mantle and rim under BSE or CL image and the increased liquid inclusion size towards the rim reflect both mineral’s staged growth under an elevated water–rock ratio. The increased Ca activity caused by enhanced interaction between fluid and Mn-containing carbonate may drive scapolite constituent change through (NaSi)-1(CaAl) substitution, creating more tetrahedral Al sites suitable for Be occupation and resulting in the increased Ca, CO32–, Be content and decreased Na content from core to rim. Precipitation of fluorite will lead to a reduce in hydrothermal Be solubility associated with a decreased fluorine activity, and favor Be to occupy the vacant T site by losing more hydrogen from the anion W site and finally form the Be-rich, Ca- and F-low vesuvianite rim. Significantly high Be, Sn, Mn and low Sr, LREE, U content at vesuvianite rim along with hydration alteration and mineralization suggest the onset of retrograde stage. Overall, the dynamic growth and epitaxially rising Be concentration of vesuvianite (∼97–1032 ppm) and scapolite (∼902–2928 ppm) recorded that the later pulsed fluid enriched Be as skarn developed, implying high grade Be mineralization tends to occur in the late magmatic-hydrothermal stage for F-rich peraluminous magmatic system.

Detrital zircon geochronology from the Nueva Segovia Schist, Nicaragua: evidence for the tectonic evolution of the Chortis Block?

Abstract The Chortis Block of Central America is a cratonic-type peri-Gondwanan terrane and is commonly included in Neoproterozoic–Paleozoic palaeogeographical reconstructions. At present, most research has focused on the Mesozoic evolution of the Chortis Block, however, its earlier history remains poorly constrained. As a result, there is considerable debate surrounding the internal complexities of the Chortis Block and its tectonothermal evolution has not been well established by geochronological and geochemical data. New field investigations from the Nueva Segovia Schist (Northern Nicaragua), considered one of the oldest exposed parts of the Chortis Block, reveal it is composed primarily of deformed sequences of greenschist facies marine clastic and chemical sediments in conformable contact with felsic volcanics. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) detrital zircon data from two samples taken from the Nueva Segovia Schist reveal a youngest age peak of c. 250 Ma with other significant peaks at c. 500 Ma, c. 1.0 Ga and c. 1.2 Ga. Taken together with field observations, these data suggest the Nueva Segovia Schist was likely deposited between c. 250 and 110 Ma proximal to Amazonia during the Late Paleozoic, and they support a Precambrian age for the basement of the East Chortis Terrane. Taken together the data support a Pangaean position of the Chortis Block, adjacent to Amazonia inboard of Oaxaquia.