Laser Ablation Multi-collector Inductively Coupled Plasma Mass Spectrometry Research Articles

Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS

Laser ablation–multi-collector–inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined 242Pu/239Pu and 240Pu/239Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for 242Pu/239Pu and from 0.183(13) to 0.577(40) for 240Pu/239Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [240Pu/239Pu = 0.388(86), 242Pu/239Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from the vicinity of the Chernobyl NPP [e.g. 240Pu/239Pu = 0.394(2) and 242Pu/239Pu = 0.027(1); Nunnemann et al. (J Alloys Compd 271–273:45–48, 1998)].Graphical Evaluation of LA-MC-ICP-MS for spatially resolving ultra-trace Pu isotopic signatures stored in environmental radioactive particles, providing new insights into the Pu isotopic distribution of the Chernobyl reactor core at the time of the accident

Geochronology, geochemistry, and geological implications of late Carboniferous – early Permian mafic and felsic intrusive rocks from Urad Zhongqi, western Inner Mongolia

AbstractThe mafic and felsic Haertaolegai intrusions crop out in Urad Zhongqi, western Inner Mongolia and are dominated by monzogranite, porphyritic granite, and gabbroic diorite intrusions. We investigate the tectonic setting, geochronology, and anorogenic characteristics of the western Inner Mongolia through field investigation, microscopic and geochemical analyses of samples from the Haertaolegai bimodal intrusions and laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) zircon U–Pb dating of gabbroic diorite and adakitic granites. Petrographic and geochemical studies of the bimodal intrusions indicate that the gabbroic diorites formed from a primary magma generated by the partial melting of lithospheric mantle material that had previously been modified by subduction-related fluids. The felsic rocks are high-K calc-alkaline and metaluminous, have characteristics of adakitic rocks and were generated during the partial melting of juvenile crustal material. Zircon U–Pb dating indicates that the felsic portion of this pluton was emplaced during late Carboniferous – early Permian time, with the mafic portion of the pluton emplaced during early Permian time. The zircons of adamellites have ɛHf(t) values andTDM2ages of +1.0 to +2.7 and 1032–1128 Ma, respectively, suggesting that they formed from magmas generated by partial melting of juvenile Mesoproterozoic lower crust. These data, combined with the geology of the region, indicate that the late Carboniferous – early Permian bimodal intrusive rocks in western Inner Mongolia record a transitional period from collisional compression to post-collisional extension. These results indicate that the Paleo-Asian Ocean in western Inner Mongolia closed before 300 Ma.

Improved Inter‐calibration of Faraday Cup and Ion Counting for In Situ Pb Isotope Measurements Using LA‐MC‐ICP‐MS: Application to the Study of the Origin of the Fangshan Pluton, North China

A laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) method was developed to obtain precise and accurate Pb isotopic ratio measurements in low‐Pb materials (< 10 μg g−1) using a combination of Faraday cups and ion counters (FC–IC). The low abundance 204Pb (~ 1.4%) was collected using an IC. A NBS 981 standard solution was used to cross‐calculate the FC–IC gain and to investigate the signal response characteristics of the IC. A significant, continuous and linear decrease in the FC–IC gain was observed within 1 hr, but this drift could be corrected using the calibrator‐sample‐calibrator bracketing method. In addition, a non‐linear response of the IC used in this study was observed and corrected by a non‐linear correction algorithm, which was established by measuring a series of gravimetrically prepared NBS 981 standard solutions (NIST SRM 981). Compared with the conventional arrangement, the use of the newly designed X skimmer cone and Jet sample cone improved the signal intensities from Pb isotopes by a factor of 1.9. Compared with only Faraday cups, using a combination FC–IC array was found to enhance the measurement repeatability (RSD) of 20xPb/204Pb by approximately one order of magnitude when the 204Pb intensity was < 8 mV. Eight natural glasses and the NIST SRM 612 reference material glass (as a calibration material) were measured to evaluate the new protocol for Pb isotope determination. The analytical results were in agreement with the reference values within 2s measurement uncertainties. For MPI‐DING ATHO‐G (5.67 μg g−1 total Pb), KL2‐G (2.07 μg g−1 total Pb) and ML3B‐G (1.38 μg g−1 total Pb), the typical accuracies of 20xPb/204Pb were 0.09% of preferred values with precisions of < 0.33% (2RSD). The Pb isotope ratios in feldspars from granodiorite and within mafic microgranular enclaves (MMEs) from the Fangshan pluton, North China, were measured using the present method. The Pb isotopic compositions of feldspars from the whole host granodiorite show that that are radiogenic in the margin zone and gradually become less radiogenic. For the MMEs, the Pb isotopic compositions of feldspars are highly variable and overlap with those of the whole host granodiorite. For single‐grain feldspar, the strong rim‐core‐rim variations of the Pb isotopic compositions and trace elements are interpreted to have been generated via magma mixing. These results suggest that the Fangshan pluton underwent magma mixing of mantle‐derived mafic magmas with felsic magmas, and the proportion of the mafic magma influx decreased over time.

Geochronological data from TTG-type rock associations of the Arroio dos Ratos Complex and implications for crustal evolution of southernmost Brazil in Paleoproterozoic times

U–Pb isotope analyses by LA-MC-ICPMS (Laser Ablation – Multi Collector – Inductively Coupled Plasma Mass Spectrometry) in zircon crystals from metatonalites, tonalites and granodiorite gneiss from the Arroio dos Ratos Complex (ARC) early magmatism in southernmost Brazil are presented. The ARC is located in the eastern portion of the Sul-rio-grandense Shield, occurring as septa and roof pendants on granitoids emplaced along the Southern Brazilian Shear Belt (SBSB). The SBSB corresponds to a translithospheric structure composed of several anastomosed shear zones of dominantly transcurrent kinematics whose syntectonic magmatism, of Neoproterozoic age, is characteristic of post-collisional environments. The studied rocks comprise TTG-type associations with coeval mafic magmatism, deformed and metamorphosed within a ductile shear zone. Zircon crystals obtained from six samples are interpreted as igneous given that the crystals are subhedral to euhedral, bipyramidal, with concentric zonation, have ratios Th/U between 0.13 and 0.81 and have restricted evidence of overgrowth. The oldest Association 1 (A1) has structures compatible with recrystallization under conditions of high temperature and an igneous age of 2148 ± 33 Ma, obtained in a metatonalite. The rocks of Association 2 (A2) have similar compositions, although with a more significant coeval mafic fraction. They are intrusive into A1 and also show high-temperature recrystallization features. However, they are less deformed and partly preserve their primary, igneous fabric. The igneous ages obtained from two A2 tonalites are 2150 ± 28 Ma and 2136 ± 27 Ma. Association 3 (A3) is represented by tonalitic to granodioritic gneisses whose structure, composition and metamorphic features are similar to those of A1 rocks, except for the absence of coeval mafic magmas in the former. Local features resulting from partial melting are present in A3 rocks. Three samples from A3 were dated. A tonalitic gneiss gives igneous age of 2099 ± 10 Ma and two granodioritic gneisses give igneous ages of 2081 ± 7 Ma and 2077 ± 13 Ma. Restricted to A1, inheritance is represented by one subhedral, zoned, gently rounded zircon crystal interpreted as igneous, of 2732 ± 40 Ma (207Pb/206Pb age), with discordance of 9% and 232Th/238U ratio of 1.17. A single Neoproteozoic metamorphic date value was obtained from the rim of a zircon crystal of Paleoproterozoic core. The age of 635 ± 6 Ma (207Pb/206Pb age), with Th/U ratio < 0.1 and 1% discordance, is interpreted as compatible with adjacent SBSB magmatism. The three associations are interpreted to represent the record of successive magmatic pulses that mark the evolution of a Paleoproterozoic continental magmatic arc. In the study area, these magmatic arc associations represent relict areas partly reworked and relatively well-preserved from Neoproterozoic tectono-magmatic post-collisional events during the construction of the Southern Brazilian Shear Belt.

An improved protocol for 87Sr/86Sr by laser ablation multi-collector inductively coupled plasma mass spectrometry using oxide reduction and a customised plasma interface

Strontium isotope analysis has become one of the most effective means to characterise mobility and migration of humans and animals in the past. Analysis of strontium isotopes in bulk dental enamel by dissolution and chemical separation is precise, reliable and accurate. Laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) offer high spatial, and therefore temporal, resolution sampling. However, the application of LA-MC-ICP-MS to strontium isotopes in bioapatites has been limited due to the presence of isobaric interferences. In particular, 40Ca31P16O+ (CaPO+) on 87Sr+ has been identified as causing a consistent positive offset in 87Sr/86Sr by LA-MC-ICP-MS, relative to dissolution methods, of approximately 500 to 1500ppm.It has been demonstrated that tuning the mass spectrometer for reduced oxide production can reduce the size of this effect but not eliminate it completely. Here we present a revised protocol using a customised plasma interface through which helium gas is introduced. We find that using the oxide reduction and the customised plasma interface protocols can further reduce the offset such that we can achieve accuracy to within typical analytical precisions (±50ppm, 2σ) without any need for further mathematical corrections. We test the methodology by ‘blind’ comparisons between LA-MC-ICP-MS and micro-drill/dissolution thermal ionisation mass spectrometry on two archaeological teeth. Both techniques are in excellent agreement.

Validation of the determination of the B isotopic composition in Roman glasses with laser ablation multi-collector inductively coupled plasma-mass spectrometry

The applicability of laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) for the determination of the B isotopic composition in Roman glasses was investigated. The δ11B values thus obtained provide information on the natron flux used during the glass-making process. The glass samples used for this purpose were previously characterized using pneumatic nebulization (PN) MC-ICP-MS. Unfortunately, this method is time-consuming and labor-intensive and consumes some 100mg of sample, which is a rather high amount for ancient materials. Therefore, the use of the less invasive and faster LA-MC-ICP-MS approach was explored. In this work, the results for 29 Roman glasses and 4 home-made glasses obtained using both techniques were compared to assess the suitability of LA-MC-ICP-MS in this context. The results are in excellent agreement within experimental uncertainty. No difference in overall mass discrimination was observed between the Roman glasses, NIST SRM 610 reference glass and B6 obsidian. The expanded uncertainty of the LA-MC-ICP-MS approach was estimated to be <2‰, which is similar to that obtained upon sample digestion and PN-MC-ICP-MS measurement.

In-situ U-Th/Pb geochronology of (urano)thorite

A laser-ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) study of seven thorite and uranothorite [(Th,U)SiO4] samples ranging in age from ∼13 to ∼500 Ma provides new insights into the U-Th/Pb isotope systematics of these geologically significant, high-Th mineral species. Despite extreme actinide enrichment and complex intra-crystal zonation in actinides and rare earth elements, this study demonstrates that radiogenic-lead loss and/or metamictization is minimal and restricted to domains that have undergone significant hydration. Dating of four igneous uranothorites yields ages that are concordant in U/Pb and Th/Pb space, consistent with other high-temperature chronometers, and are inferred to accurately reflect the timing of crystallization of each rock. Similarly, Th/Pb ages of three thorite and/or huttonite-bearing samples yield geologically plausible dates consistent with other mineral chronometers. No evidence of isotopic inheritance was observed in any of the samples. Data presented here demonstrate for the first time the feasibility of extracting accurate and precise U/Pb and Th/Pb ages from Phanerozoic thorite, uranothorite and huttonite using LA-MC-ICPMS at the 5 mm spatial resolution. These phases have the potential to be robust chronometers in igneous and metamorphic rocks as well as to provide important provenance information complementary to more widely used minerals such as detrital zircon.

Cassiterite LA-MC-ICP-MS U/Pb and muscovite 40Ar/39Ar dating of tin deposits in the Tengchong-Lianghe tin district, NW Yunnan, China

The Tengchong-Lianghe tin district in northwestern Yunnan, China, is an important tin mineralization area in the Sanjiang Tethyan Metallogenic Domain. There are three N–S trending granite belts in the Tengchong-Lianghe area, with emplacement ages ranging from Early Cretaceous to Late Cretaceous and Early Cenozoic. Tin mineralization is spatially associated with these granitic rocks. However, the petrogenetic link between the tin deposits and the host granites is not clear because of the lack of age data for the tin mineralization. We investigate the possibility of direct dating of cassiterite from three typical tin deposits in the Tengchong-Lianghe tin district, using laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). In situ LA-MC-ICP-MS dating of seven cassiterite samples from the Lailishan (LLS-1 and LLS-2), Xiaolonghe (XLH, WDS, DSP, and HJS), and Tieyaoshan (TYS) tin deposits yielded well-defined 206Pb/207Pb–238U/207Pb isochron ages. To assess the accuracy of the in situ U/Pb dating of cassiterite, 40Ar/39Ar dating of coexisting muscovite (in samples LLS-1, DSP, and TYS) was also performed. The cassiterite in situ U/Pb ages (47.4 ± 2.0, 71.9 ± 2.3, and 119.3 ± 1.7 Ma, respectively) are in excellent agreement with the coexisting muscovite 40Ar/39Ar ages (48.4 ± 0.3, 71.9 ± 1.4, and 122.4 ± 0.7 Ma, respectively). The U/Pb ages of cassiterite combined with the 40Ar/39Ar ages of muscovite indicate that there are three tin mineralization events in this district: the Lailishan tin deposit at 47.4 ± 2.0 to 52 ± 2.7 Ma, the Xiaolonghe tin deposit at 71.6 ± 2.4 to 3.9 ± 2.0 Ma, and the Tieyaoshan tin deposit at 119.3 ± 1.7 to 122.5 ± 0.7 Ma. These ages are highly consistent with the zircon U/Pb ages of the host granites. It is su.ggested that the Cretaceous tin mineralization might have taken place in a subduction environment, while the Early Tertiary tin metallogenesis was in a postcollisional geodynamic setting.

Low δ18O zircon grains in the Neoarchean Rum Jungle Complex, northern Australia: An indicator of emergent continental crust

The timing of widespread continental emergence is generally considered to have had a dramatic effect on the hydrological cycle, atmospheric conditions, and climate. New secondary ion mass spectrometry (SIMS) oxygen and laser-ablation–multicollector–inductively coupled plasma–mass spectrometry (LA-MC-ICP-MS) Lu-Hf isotopic results from dated zircon grains in the granitic Neoarchean Rum Jungle Complex provide a minimum time constraint on the emergence of continental crust above sea level for the North Australian craton. A 2535 ± 7 Ma monzogranite is characterized by magmatic zircon with slightly elevated δ18O (6.0‰–7.5‰ relative to Vienna standard mean ocean water [VSMOW]), consistent with some contribution to the magma from reworked supracrustal material. A supracrustal contribution to magma genesis is supported by the presence of metasedimentary rock enclaves, a large population of inherited zircon grains, and subchondritic zircon Hf (eHf = −6.6 to −4.1). A separate, distinct crustal source to the same magma is indicated by inherited zircon grains that are dominated by low δ18O values (2.5‰–4.8‰, n = 9 of 15) across a range of ages (3536–2598 Ma; eHf = −18.2 to +0.4). The low δ18O grains may be the product of one of two processes: (1) grain-scale diffusion of oxygen in zircon by exchange with a low δ18O magma or (2) several episodes of magmatic reworking of a Mesoarchean or older low δ18O source. Both scenarios require shallow crustal magmatism in emergent crust, to allow interaction with rocks altered by hydrothermal meteoric water in order to generate the low δ18O zircon. In the first scenario, assimilation of these altered rocks during Neoarchean magmatism generated low δ18O magma with which residual detrital zircons were able to exchange oxygen, while preserving their U-Pb systematics. In the second scenario, wholesale melting of the altered rocks occurred in several distinct events through the Mesoarchean, generating low δ18O magma from which zircon crystallized. Ultimately, in either scenario, the low δ18O zircons were entrained as inherited grains in a Neoarchean granite. The data suggest operation of a modern hydrological cycle by the Neoarchean and add to evidence for the increased emergence of continents by this time.

Guidelines for reporting zircon Hf isotopic data by LA-MC-ICPMS and potential pitfalls in the interpretation of these data

Technical Paper High quality analytical data are essential for the development of sound scientific interpretations. To ensure the quality of the data published in Chemical Geology, a new type of contribution has been introduced - the Invited Technical Paper. When a particular technical issue needing discussion or clarification is identified, specialists in the technique will be invited to share their expertise. As is true for all articles published in the journal, these contributions will be subject to peer review before publication. The first topic to be treated concerns in situ Hf isotopic measurements in zircon by laser ablation inductively coupled plasma mass spectrometry. This is an extremely powerful and promising technique that has been adopted by many laboratories throughout the world. However, if insufficient care is taken during analysis and data processing, inaccurate results can be obtained, notably because of the existence of very large isobaric interferences on the isotope of interest. To address this issue, we have asked Christopher Fisher, Jeffery Vervoort and John Hanchar to provide a set of guidelines that can be adopted to assure that reliable Hf isotopic data are obtained by this technique. Abstract Over the past decade, the Hf isotope composition of zircon, as determined in situ by laser ablation-multicollector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS), has been applied increasingly to a wide range of geological problems and has proven to be a valuable analytical tool. There has been no uniformity, however, in the reporting of in situ Hf isotopic data and, quite often, reviewers and readers of papers are not provided with sufficient information to assess data quality. The goal of this invited contribution is to provide the non-specialist with a brief outline and explanation of what is required for proper presentation and documentation of in situ Hf isotopic data from zircon, including details of how the challenging large isobaric interference corrections have been made. In addition, we discuss a number of potential pitfalls vis-a-vis the assignment of the incorrect age to the measured Hf isotope composition. Non-specialists should be aware of these important issues when doing their own analyses and evaluating the analyses done by others.

Lead Isotopic Composition of Trinitite Melt Glass: Evidence for the Presence of Canadian Industrial Lead in the First Atomic Weapon Test

The Pb isotopic compositions for 51 spots of melt glass in 11 samples of trinitite have been determined by laser ablation multicollector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Trinitite glass yields a large range of Pb isotopic compositions (i.e., (206)Pb/(204)Pb = 17.08-19.04), which reflect mixing between industrial Pb from materials used in the Trinity test and natural geologic components. Areas within trinitite melt glass containing high concentrations of both Cu and Pb, which are derived from the bomb and blast site-related components, were used for delineating the Pb isotopic composition corresponding to the anthropogenic Pb component. Comparison between the isotopic composition estimated here for the industrial Pb used in the Trinity test and those from known Pb deposits worldwide indicates close agreement with ore from the Buchans mine (Newfoundland, Canada). The Buchans mine was active during the time of the Trinity test and was operated by the American Smelting and Refining Company, which could have provided the Pb used in the test. The industrial Pb used in the Trinity test materials is not documented in the literature (or declassified) but could have been present in bricks, solder, pigs, or some other anthropogenic component related to the experiment.

U-Pb zircon age of the youngest magmatic activity in the High Tatra granites (Central Western Carpathians)

Abstract Detailed cathodoluminescence (CL) imaging of zircon crystals, coupled with Laser Ablation Multi-Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS) U-Pb zircon dating was used to develop new insights into the evolution of granitoids from the High Tatra Mountains. The zircon U-Pb results show two distinct age groups (350±5 Ma and 337±6 Ma) recorded from cores and rims domains, respectively. Obtained results point that the last magmatic activity in the Tatra granitoid intrusion occurred at ca. 330 Ma. The previously suggested age of 314 Ma reflects rather the hydrothermal activity and Pb-loss, coupled with post-magmatic shearing.

Orogen‐parallel ductile extension and extrusion of the Greater Himalaya in the late Oligocene and Miocene

AbstractPredominant stretching structures in the Greater Himalayan Crystalline Complex (GHC) trend perpendicular to the belt and are linked to the southward exhumation or emplacement of the GHC between the South Tibet Detachment (STD) and the Main Central Thrust. However, our field investigations in southern Tibet reveal the widespread presence of gently dipping shear zones with a penetrative orogen‐parallel stretching lineation, which separates the Tethyan Himalayan Sequence and the underlying GHC. The shear zones are well preserved in the upper part of the GHC, south to and structurally lower than the STD. Field criteria, microstructures, and quartz fabrics indicate top‐to‐the‐east shearing in the Yadong shear zone (eastern GHC), coexistence of top‐to‐the‐east and top‐to‐the‐west shearing in the Nyalam shear zone (central GHC), but top‐to‐the‐west shearing in the Pulan shear zone (western GHC). Characteristic microstructures and slip systems of quartz in the high‐grade GHC rocks resulted from the lateral flow under upper amphibolite (up to 650–700 °C) to greenschist facies conditions. U‐Pb ages of metamorphic zircon rims by sensitive high‐resolution ion microprobe (SHRIMP) and laser ablation multi‐collector inductively coupled plasma mass spectrometry (LA‐MC‐ICP‐MS) analyses yield 28–26 Ma for the initiation of the Yadong and Nyalam shear zones and 22–15 Ma for the activation of the Pulan shear zone. In addition, 40Ar/39Ar cooling ages of biotite and muscovite suggest cessation of ductile sharing at 13–11 Ma on the Yadong shear zone, which is coeval with the activation of the STD. Combined with previous studies, we propose that initiation of orogen‐parallel extension marks the transition from burial/crustal thickening to exhumation of the GHC. Due to lateral crustal thickness gradients in a thickened crust, orogen‐parallel gravitational collapse occurred within the convergent Himalayan orogen in the late Oligocene‐Miocene. This tectonic denudation triggered and enhanced partial melting and ductile extrusion of the GHC in the Miocene.

Petrogenesis of Ordovician magmatic rocks in the southern Chiapas Massif Complex: relations with the early Palaeozoic magmatic belts of northwestern Gondwana

The recent discovery of Early Ordovician S-type granites in the southwest of the Chiapas Massif Complex adds a new perspective to the Palaeozoic history of the Maya block, inasmuch as no rocks of such age had previously been reported in this region. New geologic mapping west of Motozintla, Chiapas, revealed pelitic to psammitic metasedimentary successions (Jocote Unit) intruded by granitoids and metabasites. The Jocote Unit is unconformably underlain by the newly defined Candelaria Unit, which comprises deformed calc-silicate rocks and interlayered folded amphibolites. The Candelaria Unit is the oldest rock succession so far recognized in the southern Maya block. We used laser-ablation multicollector inductively coupled plasma mass spectrometry (LA-ICP-MS) U–Pb dating to determine the ages of the rock, yielding Early Ordovician (ca. 470 Ma) and Late Ordovician (ca. 450 Ma) ages. Major and trace element geochemistry, as well as Nd and Sr isotope data, suggest that folded amphibolites of the Candelaria Unit are mantle-derived and are probably related to rifting. The Early Ordovician bimodal magmatism of the Jocote Unit is more strongly differentiated; it reflects crustal contamination and volcanic-arc chemical signatures. A granitic stock (Motozintla pluton) intruded the area in the Late Ordovician. Its geochemical composition indicates less crustal contamination and a mixed signature between volcanic-arc and within-plate settings. Magmatic rocks analogous in age and chemical character crop out in the Rabinal and the Altos Cuchumatanes areas of Guatemala, suggesting the existence of a semi-continuous Ordovician magmatic belt from Chiapas to central Guatemala. Similar but somewhat younger granites also occur in the Maya Mountains of Belize, suggesting that magmatism migrated in the Silurian from the Chiapas–Guatemala belt towards the Maya Mountains.

Two detrital zircon signatures for the Cambrian passive margin of northern Laurentia highlighted by new U-Pb results from northern Canada

In time, Laurentia was bounded on all sides by passive margins, providing an opportunity to establish a Cambrian of detrital zircon provenance for the craton during a relatively quiescent tectonic stage. U-Pb detrital zircon ages from laser ablation–multicollector–inductively coupled plasma–mass spectrometry (LA-MC-ICP-MS) and sensitive high-resolution ion microprobe (SHRIMP) analysis of seven sandstone samples from northern Northwest Territories are consistent with generally local provenance. Samples from Mackenzie Mountains were most likely derived from the Proterozoic Mackenzie Mountains Supergroup and are dominated by detrital zircon ages of ca. 1020–1516 Ma, but also contain populations of ca. 1615–1692 Ma and ca. 2699–2752 Ma. sandstones from south of Great Bear Lake have a complementary set of detrital zircon age populations dominated by ca. 1810–2010 Ma, with smaller relative probability peaks at 2100 Ma, 2300 Ma, and 2600 Ma, which are consistent with derivation from the Hottah terrane, Great Bear magmatic zone, and Slave craton. Comparison of the signatures from Mackenzie Mountains and Great Bear Lake south suggests that there were two distinct sources of detrital zircon available to the northern Northwest Territories during the Cambrian. Detrital zircon ages from strata of Victoria Island appear to be a mixture of Shaler Supergroup, Slave craton–like, Taltson-Thelon orogen, and Wopmay orogen sources. Following the dichotomy of detrital zircon age spectra presented by samples from Mackenzie Mountains and Great Bear Lake south allows subdivision of other published detrital zircon ages from across northern Laurentia into two groups: Laurentia type 1 suite reflects the Archean cratons and Paleoproterozoic orogens of the Precambrian Shield. Laurentia type 2 suite is dominated by Grenvillian and older ages (1000–1500 Ma) and includes relative probability peaks at 1600–1700 Ma and 2700–2750 Ma. We find, therefore, that this baseline mirrors the Precambrian tectonic fabric of Laurentia from Archean cratonization and Paleoproterozoic through Mesoproterozoic orogenesis, culminating in assembly of the supercontinent Rodinia. Furthermore, the Neoproterozoic breakup of Rodinia and establishment of passive margins surrounding Laurentia provided little new zircon available to the sedimentary system. The detrital zircon spectra for the of northern Laurentia are intended to provide a reference to test the affinity of suspect terranes and potentially exotic detrital zircon within Paleozoic foreland basins.

Conditions of Mytilus edulis extracellular body fluids and shell composition in a pH‐treatment experiment: Acid‐base status, trace elements and δ11B

Mytilus edulis were cultured for 3 months under six different seawater pCO2 levels ranging from 380 to 4000 μatm. Specimen were taken from Kiel Fjord (Western Baltic Sea, Germany) which is a habitat with high and variable seawater pCO2 and related shifts in carbonate system speciation (e.g., low pH and low CaCO3 saturation state). Hemolymph (HL) and extrapallial fluid (EPF) samples were analyzed for pH and total dissolved inorganic carbon (CT) to calculate pCO2 and [HCO3−]. A second experiment was conducted for 2 months with three different pCO2 levels (380, 1400 and 4000 μatm). Boron isotopes (δ11B) were investigated by LA‐MC‐ICP‐MS (Laser Ablation–Multicollector–Inductively Coupled Plasma–Mass Spectrometry) in shell portions precipitated during experimental treatment time. Additionally, elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF of specimen from the second experiment were measured via ICP‐OES (Inductively Coupled Plasma–Optical Emission Spectrometry). Extracellular pH was not significantly different in HL and EPF but systematically lower than ambient water pH. This is due to high extracellular pCO2 values, a prerequisite for metabolic CO2 excretion. No accumulation of extracellular [HCO3−] was measured. Elemental ratios (B/Ca, Mg/Ca and Sr/Ca) in the EPF increased slightly with pH which is in accordance with increasing growth and calcification rates at higher seawater pH values. Boron isotope ratios were highly variable between different individuals but also within single shells. This corresponds to a high individual variability in fluid B/Ca ratios and may be due to high boron concentrations in the organic parts of the shell. The mean δ11B value shows no trend with pH but appears to represent internal pH (EPF) rather than ambient water pH.

Flysch deposition and preservation of coherent bedding in an accretionary complex: Detrital zircon ages from the Upper Cretaceous Valdez Group, Chugach terrane, Alaska

The Upper Cretaceous Valdez Group represents the flysch facies of the Mesozoic Chugach terrane accretionary complex in southern Alaska. The Valdez Group is dominated by litharenite sandstone and argillite deposited as coherent beds, unlike the older McHugh Complex melange and massive sandstones. Detrital zircons from five sandstones sampled along an ∼55 km transect through the Valdez Group were dated using U-Pb laser ablation–multicollector–inductively coupled plasma–mass spectrometry (LA-MC-ICP-MS). The youngest populations from the two oldest samples, located along strike from each other, were 82–81 Ma. Three samples across strike and outboard of the others are separated by ∼50 km, but each has a youngest population dated at ca. 68 Ma. All of these samples have major grain population ages that suggest erosion from the Coast Mountains Batholith, consistent with petrography and grain modes suggesting an arc source. No apparent age gap exists between the youngest McHugh Complex samples and the oldest Valdez Group samples, suggesting continuous deposition despite the different depositional and tectonic style. We propose a model in which the onset of coherently bedded flysch marks the transition from deposition in the trench or trench slope to deposition on the oceanic plate beyond the trench after it was filled at ca. 84 Ma, i.e., the time of the youngest melange sedimentation. Preservation of coherent bedding resulted as large coherent blocks of Valdez Group rocks were imbricated into the subduction complex during continued subduction in Paleogene time.

Tracing the provenance and recrystallization processes of the Earth's oldest detritus at Mt. Narryer and Jack Hills, Western Australia: An in situ Sm–Nd isotopic study of monazite

Mount Narryer and Jack Hills metasedimentary rocks in the Narryer Gneiss Complex of the Yilgarn Craton, Western Australia, contain zircons with ages up to 4.4 Ga, the oldest known crustal materials on Earth, and monazites up to 3.6 Ga. In this study, we have investigated 147Sm– 143Nd systematics of detrital and metamorphic monazites from these metasedimentary rocks using laser ablation-multicollector-inductively coupled plasma mass spectrometry (LA-MC-ICPMS). All detrital monazites have negative initial εNd(t) values, indicating that their parental magmas formed by remelting of older crustal materials. A comparison between the initial εNd(t) values of the detrital monazites and granitoids in the Narryer Gneiss Complex indicates that the Mt. Narryer and Jack Hills sediments were partly derived from the most isotopically enriched surrounding granitoids with ages of ca. 3.6 and 3.3 Ga. The metamorphic monazites generally have lower initial εNd(t) values when compared to the detrital monazites. However, the detrital and metamorphic monazites show similar distributions of εNd(t) at the ages of sediment deposition (3.28 Ga for Mt. Narryer and 3.05 Ga for Jack Hills). In addition, multiple analyses on single monazite grains having core-rim structures reveal that the cores and the recrystallized rims had identical Nd isotopic compositions at the time of recrystallization. These findings indicate that older monazites are source of light rare earth elements for younger metamorphic monazite formation and, therefore, that monazite can inherit its primary Sm–Nd isotopic signature during the recrystallization processes. We calculated the Nd model ages for all analyzed monazites to estimate crustal residence time of their source materials. We find that no igneous monazites older than 4.0 Ga were recrystallized to form the monazites. This implies that the lack of Hadean monazites is not due to recrystallization of ancient monazites during later metamorphism, but due to high-Ca compositions of the parental magmas of Hadean detritus, which prevent growth of magmatic monazite.

Synthetic zircon doped with hafnium and rare earth elements: A reference material for in situ hafnium isotope analysis

A series of flux-grown synthetic zircon crystals doped with Hf and selected rare earth elements (REE) were produced for use as a potential reference material for Lu–Hf isotopic analysis of zircon by in situ laser ablation multi-collector inductively-coupled plasma mass spectrometry (LA-MC-ICPMS). The synthetic zircon crystals were doped such as to produce a large range of REE/Hf, allowing for a robust means of monitoring and correcting the sometimes large 176Yb and 176Lu isobaric interferences on the low-abundance 176Hf in natural zircon, as well as potential oxide interferences from Gd, Tb, and Dy. The synthetic zircon crystals have a homogeneous Hf isotopic composition, both within and between grains, as documented by solution MC-ICPMS analyses of Hf chemically separated from multiple fragments of zircon from three different syntheses, and 321 laser ablation MC-ICPMS analyses done in two different laboratories. An additional 110 in situ analyses of natural zircon crystals reveal identical behavior of natural and synthetic zircon during Hf isotope analysis by laser ablation. Hence, the synthetic zircon crystals provide a means of monitoring a wide range of Yb and Lu interferences (up to 50% of the total signal intensity at mass 176) during routine isotopic analysis for geological studies. They also may be helpful in developing improved laboratory protocols for accurate in situ Lu–Hf isotopic measurement of natural zircon. The present data illustrate the importance of the 176Yb interference correction on 176Hf, which can result in large biases if not properly applied to natural samples with their variable and often high 176Yb/ 177Hf. This study definitively shows that use of high-REE/Hf synthetic zircon standards for calibrating the Yb mass bias correction is more accurate than use of Yb-doped natural Hf solutions. Finally, the results of the present work suggest that synthetic minerals may prove useful as both in situ method development tools and isotopic reference materials.

Using pegmatite geochronology to constrain temporal events in the Adirondack Mountains

U-Pb laser ablation–multicollector–inductively coupled plasma–mass spectrometry (LA-MC-ICP-MS) ages have been determined from large zircon crystals separated from pegmatites of the Adirondack Mountains, New York. Emplacement and metamorphic ages ranging from 949 ± 10 to 1222 ± 12 Ma help constrain the timing of igneous, metamorphic, and deformational history of the region, and are associated with Shawinigan, Ottawan, and Rigolet orogenesis. Geologically reasonable ages were obtained from most zircon separates despite large size, a limited number of grains, high uranium and thorium contents, dark and opaque interiors, high density of fractures, and widespread areas of metamictization and Pb loss. However, few grains show zoning or differences in composition when viewed with the backscattered mode on the scanning electron microscope. Large, clear, internally featureless, U-poor grains yield the best constrained ages. U-Th-Pb monazite ages, determined by electron probe, vary from 874 ± 27 Ma to 297 ± 62; the younger age may reflect the timing of hydrothermal fluid infiltration related to late Acadian events. This study suggests that, with appropriate care, zircons from pegmatites are a reasonable target for LA-MC-ICP-MS geochronology, widening the current arsenal of sampling targets.