Short communication: On the potential use of materials with heterogeneously distributed parent and daughter isotopes as primary standards for non-U-Pb geochronological applications of laser ablation inductively coupled mass spectrometry (LA-ICP-MS)

Many new geochronological applications of laser ablation inductively coupled mass spectrometry (LA-ICP-MS) have been proposed in recent years. One of the problems associated with this rapid growth is the lack of chemically and isotopically homogeneous matrix-matched primary standards to control elemental fractionation during LA-ICP-MS analysis. In U-Pb geochronological applications of LA-ICP-MS this problem is often addressed by utilising matrix-matched primary standards with variable chemical and isotopic compositions. Here I derive a set of equations to adopt this approach for non-U-Pb geochronological applications of LA-ICP-MS.

Trace precious metals in major sulfide minerals from the Federova Tundra platinum group element deposit in the Fedorova-Pana layered intrusion, central Kola Peninsula, Russia

ABSTRACT Drill-core samples from the basal Cu-Ni-platinum-group element mineralization of the Early Proterozoic Fedorova Tundra intrusion in the Fedorova-Pana layered intrusion, central Kola Peninsula, Russia, were studied in two separate projects in Canada and Russia. In Canada, trace precious metal analyses by laser ablation inductively coupled mass spectrometry of 323 base metal sulfide particles [pentlandite (101), pyrrhotite (98), chalcopyrite (25), and pyrite (99)] show that Pd is highly concentrated in pentlandite. Most of the analyses (71%) were done using two master composite samples of comminuted drill core representative of the West Pit and East Pit mineralization, FWMC and FEMC, respectively. Fewer analyses were made of three other comminuted drill core samples from the West Pit referred to as “lithology” samples: OLFW (olivine-bearing rocks), ANFW (leucocratic rocks), and GNFW (gabbronorite). In Russia, 120 polished sections sliced from drill core from the West and East Pits and from four other Fedorova Tundra intrusion deposits (Kievey, Northern Kamennik, Eastern Chuarvy, and Southern Kievey) were studied mineralogically. Platinum group mineral characterization and trace Pd electron probe microanalyses of pentlandite were done using polished sections from all six locations (n = 95). The trace electron probe microanalysis data for Pd in pentlandite from the West (n = 35) and East (n = 19) Pit samples, though at much higher detection levels, are considered to be comparable to the laser ablation inductively coupled mass spectrometry data. The Eastern Chuarvy samples show particularly high Pd concentrations averaging 0.49 wt.% Pd (n = 11) and as high as 1.64 wt.% Pd. The combined data from these studies guides our estimate that pentlandite accounts for 30 to 50% of the Pd in these ores and that Rh solid solution in sulfides may account for >98% of the total Rh.

Strengths and limitations of in situ U-Pb titanite petrochronology in polymetamorphic rocks: An example from western Maine, USA.

Titanite is a potentially powerful U-Pb petrochronometer that may record metamorphism, metasomatism, and deformation. Titanite may also incorporate significant inherited Pb, the correction for which may introduce inaccuracies and result in geologically ambiguous U-Pb dates. Here we present laser ablation inductively coupled mass spectrometry (LA-ICP-MS)-derived titanite U-Pb dates and trace element concentrations for two banded calc-silicate gneisses from south-central Maine, USA (SSP18-1A & -1B). Single spot common Pb-corrected dates range from 400 to 280 Ma with 12–20 Ma propagated 2SE. Titanite in sample SSP18-1B exhibit regular core-to-rim variations in texture, composition, and date. We identify four titanite populations: 1) 399 ± 5 Ma (95 % CL) low Y + HREE cores and mottled grains, 2) 372 ± 7 Ma high Y + REE mantles and cores, 3) 342 ± 6 Ma cores with high Y + REE and no Eu anomaly, and 4) 295 ± 6 Ma LREE-depleted rims. We interpret the increase in titanite Y + HREE between ca. 400 and ca. 372 Ma to constrain the timing of diopside fracturing and recrystallization and amphibole breakdown. Apparent Zr-in-titanite temperatures (803 ± 36 °C at 0.5 ± 0.2 GPa) and increased XDi suggest a thermal maximum at ca. 372 Ma. Population 3 domains dated to ca. 342 Ma exhibit no Eu anomaly and are observed only in compositional bands dominated by diopside (> 80 vol %), suggesting limited equilibrium between titanite and plagioclase. Finally, low LREE and high U/Th in Population 4 titanite date the formation of hydrous phases, such as allanite, during high XH2O fluid infiltration at ca. 295 Ma. In contrast to the well-defined date-composition-texture relationships observed for titanite from SSP18-1B, titanite grains from sample SSP18-1A exhibit complex zoning patterns and little correlation between texture, composition, and date. We hypothesize that the incorporation of variable amounts of radiogenic Pb from dissolved titanite into recrystallized domains resulted in mixed ages spanning 380–330 Ma. Although titanite may reliably record multiple phases of metamorphism, these data highlight the importance of considering U-Pb data along with chemical and textural data to screen for inherited radiogenic Pb.

First U-Pb dating of fossilized soft tissue using a new approach to paleontological chronometry

Previous U-Pb dating of fossils has had only limited success because of low uranium content and abundance of common Pb as well as element mobility during late diagenesis. We report the first accurate U-Pb dating of fossilized soft tissue from a Pliocene phosphatized bivalve mold using laser ablation–inductively coupled mass spectrometry (LA-ICPMS). The fossilized soft tissue yields a diagenetic U-Pb age of 3.16 ± 0.08 Ma, which is consistent with its late Pliocene stratigraphy and similar to the oldest U-Pb age measured on accompanying shark teeth. Phosphate extraclasts give a distinctly older age of 5.1 ± 1.7 Ma, indicating that they are likely detrital and may have furnished P, promoting phosphatization of the mold. The U-Pb ages reported here along with stratigraphic constraints suggest that diagenesis occurred shortly after the death of the bivalve and that the U-Pb system in the bivalve mold remained closed until the present. Shark teeth collected from the same horizon show variable resetting due to late diagenesis. Data were acquired as line scans in order to exploit the maximum Pb/U variation and were regressed as counts, rather than ratios, in three-dimensional space using a Bayesian statistical method.

Expanding Limits of Laser-Ablation U-Pb Calcite Geochronology

U-Pb geochronology of calcite by laser-ablation inductively-coupled mass spectrometry (LA-ICMPS) is an emerging field with potential to solve a vast array of geologic problems. Because of low levels of U and Pb, measurement by more sensitive instruments, such as those with multiple collectors (MC), is advantageous. However, whereas measurement of traditional geochronometers (e.g., zircon) by MC-ICPMS has been limited by detection of the daughter isotope, U-Pb dating of calcite can be limited by detection of the parent isotope, if measured on a Faraday detector. The Nu P3D MC-ICPMS employs a new detector array to measure all isotopes of interest on Daly detectors. A new method, described herein, utilizes the low detection limit and high dynamic range of the Nu P3D for calcite U-Pb geochronology, and compares it with traditional methods. A model is created to explore the limits of U, Pb, and U/Pb ratios that can be measured by LA-ICPMS and can serve as a guide to evaluate potential candidate materials for geochronology.

Evaluation of a Novel Boron-Containing α-d-Mannopyranoside for BNCT

Boron neutron capture therapy (BNCT) is a unique anticancer technology that has demonstrated its efficacy in numerous phase I/II clinical trials with boronophenylalanine (BPA) and sodium borocaptate (BSH) used as 10B delivery agents. However, continuous drug administration at high concentrations is needed to maintain sufficient 10B concentration within tumors. To address the issue of 10B accumulation and retention in tumor tissue, we developed MMT1242, a novel boron-containing α-d-mannopyranoside. We evaluated the uptake, intracellular distribution, and retention of MMT1242 in cultured cells and analyzed biodistribution, tumor-to-normal tissue ratio and toxicity in vivo. Fluorescence imaging using nitrobenzoxadiazole (NBD)-labeled MMT1242 and inductively coupled mass spectrometry (ICP-MS) were performed. The effectiveness of BNCT using MMT1242 was assessed in animal irradiation studies at the Kyoto University Research Reactor. MMT1242 showed a high uptake and broad intracellular distribution in vitro, longer tumor retention compared to BSH and BPA, and adequate tumor-to-normal tissue accumulation ratio and low toxicity in vivo. A neutron irradiation study with MMT1242 in a subcutaneous murine tumor model revealed a significant tumor inhibiting effect if injected 24 h before irradiation. We therefore report that 10B-MMT1242 is a candidate for further clinical BNCT studies.

Evaluation of 24-h urine containers for urine copper measurement by inductively coupled plasma mass spectrometry

Objective To determine the necessity for acid-washed containers for 24-h urine copper analysis. Methods Copper solutions, with concentrations relevant to clinical decision limits, were prepared by spiking both assay diluent and unknown urine samples with the copper calibrator. Samples were split between plain and acid-washed 24-h urine containers, and copper analysis was performed using inductively coupled mass spectrometry (ICP-MS). Results Measurement of copper in both spiked diluent and spiked urine samples showed minimal concentration bias between acid-washed and plain 24-h urine containers. Conclusions Acid-washed containers are not required for the measurement of copper in 24-h urine samples.

A new rapid treatment of human hair for elemental determination by inductively coupled mass spectrometry

Advancements in sample preparation for performing elemental analysis are coming from the dissemination of microwave-assisted procedures, but there is still room for improvements by looking for fast and easily applicable procedures.