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Creators/Authors contains: "Stone, JS"

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  1. Throughout the course of an organism’s life, the chemical signatures of environment, food consumption, and weather are recorded into their carbonate structures; these signatures can be directly linked to a time-resolved lifespan. Here we present trace element data from benthic foraminifera and tropical molluscs determined using an ESI NWR193UC excimer laser coupled with an Agilent 8900 triple quadrupole mass spectrometer in the MicroAnalytical Geochemistry and Isotope Characterization (MAGIC) Laboratory at the University of Maine. Benthic foraminifera are protists that live on the sea floor and produce calcite shells, progressively adding chambers. Changes in Mg/Ca in foraminifera are used as a proxy for ocean temperature. Laser ablation ICP-MS data for 18 trace elements were collected in individual growth chambers in foraminifera of the genus Uvigerina from the Bay of Plenty. Line scans were performed within thin (~10 µm) chamber walls using a spot size of 8 µm, beam energy density of 3 J/cm2, repetition rate of 12 Hz, and scan speeds of 2-3 µm/s. Concentrations were determined relative to the NIST610 glass. Ratios of Mg/Ca and other trace elements record the same range of values as those determined via bulk wet chemistry analysis of ~10 foraminifera for a given population, which suggests that LA-ICP-MS may be a viable alternative to wet chemistry. Trace element data were collected across shells of the warm-tropical mollusc species Chione subrugosa from the Ostra Base Camp area, Peru (78°37’22”W, 8°54’46”S). Previous studies of the area have suggested that a large climate transition occurred, transforming a warm water tropical bay into a desert surrounded by a coastal stand with cool waters. This area was occupied by humans at 6250-5450 radiocarbon years BP. This study examines Chione subrugosa, which were found in the living position at the fossilized Ostra Beach and are thought to have been the final living warm-tropical molluscs in the bay. Studies of modern molluscs have revealed that molluscs record massive climatic changes, such as El Niño, in their chemistry. Laser ablation provides a unique opportunity to examine chemical changes directly related to the changing coastal environment. Line scans transverse growth bands along the length of the shell, providing a high resolution record of daily variation in trace element chemistry over the lifespan of the mollusc. Eleven elements were analysed with a beam energy density of 2.4 J/cm2, repetition rate of 15 Hz, spot size of 5 x 25 µm, and a scan speed of 5 µm/s. Preliminary data suggest the preservation of yearly oscillations in trace elements, with high concentrations of La, Ce, U, and Pb during early shell growth. Continued study will examine catastrophic mollusc life events in an effort to link these with environmental climate changes over daily timescales. 
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  2. Titanite and apatite can incorporate significant amounts of common Pb (204Pb) into their mineral structures, which leads to uncertainty when applying the U-Pb decay series for geochronology. The isobaric interference between 204Pb and 204Hg creates an additional complexity when calculating common lead corrections. Here we investigate the removal of 204Hg interferences during titanite U-Pb dating using reaction cell gas chemistry via triple quadrupole mass spectrometry compared with traditional methods that calculate U-Pb ages using a common lead correction. U-Pb dates for titanite natural reference materials MKED-1 and BLR-1 were determined using an ESI NWR193UC excimer laser coupled with an Agilent 8900 ‘triple quadrupole’ mass spectrometer. The 8900 is equipped with an octopole collision/reaction cell, which enables online interference removal. In order to compare traditional methods for U-Pb dating with interference removal methods, two experiments were run, one in which data was collected in NoGas mode, and one in which the 8900 was run in MS/MS mode, in order to assess the feasibility of determining U/Pb ratios with mass shifted isotopes. In MS/MS mode, NH3 was flowed through the reaction cell in order to enable a charge transfer reaction between NH3 and Hg+, effectively neutralizing Hg. During spot analyses in NoGas mode, masses 202Hg, 204Hg, 204Pb, 206Pb, 207Pb, 208Pb, 232Th, 235U, and 238U were monitored. For spot analyses in MS/MS mode, Th and U isotopes were measured on-mass at 232Th, 235U, 238U and mass-shifted to 247Th, 250U, and 253U. Pb isotopes were measured on-mass since Pb does not react with NH3. Ratios for 207Pb/235U, 206Pb/238U, and 207Pb/206Pb were calculated in Iolite (v.3.7.1) using the Geochron4 DRS using MKED-1 as the primary reference material and BLR-1 as a secondary reference material. Dates were calculated using IsoplotR. Weighted mean ages for titanite BLR-1 in MS/MS mode are 1043.8 ± 10.5 Ma (2σ, MSWD=1.08) for U isotopes measured on mass, and 1039.7 ± 8.3 Ma (2σ, MSWD=1.08) for mass-shifted U isotopes. These dates are both in agreement with the TIMS 206Pb/238U date for the BLR-1 titanite of 1047.1 ± 0.4 Ma. The use of NH3 for reaction cell chemistry has the potential to enable measurement of 204Pb without needing to correct for Hg interferences. 
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