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1. U-Pb dating of titanite by LA-ICP-QQQ-MS

   Stone, Joshua S; Cruz-Uribe, AM; Brooks, HL (May 2019, North American Workshop on Laser Ablation 2019 Abstracts)

   Titanite has the ability to incorporate significant amounts of common Pb, which leads to uncertainty when applying the U-Pb decay series for geochronology. The isobaric interference of 204Hg on 204Pb poses an additional complexity in applying common Pb corrections. Here we investigate the removal of 204Hg interferences during titanite U-Pb dating using reaction cell gas chemistry via triple quadrupole mass spectrometry. U-Pb dates were determined for the natural titanite reference materials MKED-1 and BLR1 using an ESI NWR193UC excimer laser coupled to an Agilent 8900 ‘triple quad’ mass spectrometer. The 8900 is equipped with an octopole collision/reaction cell, which enables online interference removal. Two experiments were run, one in which we collected data in NoGas mode, and one in which NH3 was used as a reaction cell gas in MS/MS mode, in order to assess the feasibility of determining U/Pb ratios with mass shifted isotopes. In all experiments, a signal smoothing device was placed inline just before the ICP-MS interface, downstream from the addition of the Ar nebulizer gas to the He carrier gas stream. For the NoGas experiment, titanite was ablated using a 25 µm spot, with a beam energy density of 3 J/cm2, and a pulse rate of 4 Hz. In NoGas mode, signal intensities for the isotopes 201Hg, 202Hg, 204Pb, 206Pb, 207Pb, 232Th, 235U, and 238U were counted. In MS/MS mode, titanite was ablated using a 40 µm spot, with a beam energy density of 5 J/cm2, and a pulse rate of 4 Hz. A larger spot size in this experiment was used to counteract the decrease in signal intensity due to use of the reaction cell. 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. The isotopes 201Hg, 202Hg, 204Pb, 206Pb, and 207Pb were measured on-mass, as the isotopes of Pb are not affected by the NH3 gas. Uranium and Th both exhibit partial reaction with NH3 gas; therefore, the isotopes 232Th, 235U, and 238U were measured mass-shifted up 15 mass units, at masses 247, 250, and 253 respectively. Ratios of 207Pb/235U, 206Pb/238U, and 207Pb/206Pb were determined using the UPbGeochron4 DRS in Iolite (v.3.71) with MKED-1 as the primary reference material. Dates were calculated using IsoplotR by applying the Stacey-Kramers correction for common Pb. All isotopes of Hg were effectively neutralized by the NH3 charge transfer reaction in MS/MS mode; zero counts were detected for Hg isotopes. Dates for the BLR-1 titanite were 1050.55 ± 2.72 (2σ, n=12) Ma in NoGas mode, and 1048 ± 1.88 (2σ, n=15) Ma in MS/MS mode. These dates are in excellent agreement with the TIMS 206Pb/238U date for the BLR-1 titanite of 1047.1 ± 0.4 Ma. This method has the potential to enable measurement of 204Pb without needing to correct for Hg interferences. 

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2. Minimizing the effects of Pb loss in detrital and igneous U–Pb zircon geochronology by CA-LA-ICP-MS

   https://doi.org/10.5194/gchron-6-89-2024  

   Donaghy, Erin E.; Eddy, Michael P.; Moreno, Federico; Ibañez-Mejia, Mauricio (March 2024, Geochronology)

   Ascough, P.; Dunai, T.; King, G.; Lang, A.; Mezger, K. (Ed.)

   Detrital zircon geochronology by laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) is a widely used tool for determining maximum depositional ages and sediment provenance, as well as reconstructing sediment routing pathways. Although the accuracy and precision of U–Pb geochronology measurements have improved over the past 2 decades, Pb loss continues to impact the ability to resolve zircon age populations by biasing affected zircon toward younger apparent ages. Chemical abrasion (CA) has been shown to reduce or eliminate the effects of Pb loss in zircon U–Pb geochronology but has yet to be widely applied to large-n detrital zircon analyses. Here, we assess the efficacy of the chemical abrasion treatment on zircon prior to analysis by LA-ICP-MS and discuss the advantages and limitations of this technique in relation to detrital zircon geochronology. We show that (i) CA does not systematically bias LA-ICP-MS U–Pb dates for 13 reference materials that span a wide variety of crystallization dates and U concentrations, (ii) CA-LA-ICP-MS U–Pb zircon geochronology can reduce or eliminate Pb loss in samples that have experienced significant radiation damage, and (iii) bulk CA prior to detrital zircon U–Pb geochronology by LA-ICP-MS improves the resolution of age populations defined by 206Pb/238U dates (Neoproterozoic and younger) and increases the percentage of concordant analyses in age populations defined by 207Pb/206Pb dates (Mesoproterozoic and older). The selective dissolution of zircon that has experienced high degrees of radiation damage suggests that some detrital zircon age populations could be destroyed or have their abundance significantly modified during this process. However, we did not identify this effect in either of the detrital zircon samples that were analyzed as part of this study. We conclude that pre-treatment of detrital zircon by bulk CA may be useful for applications that require increased resolution of detrital zircon populations and increased confidence that 206Pb/238U dates are unaffected by Pb loss. 

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3. Uncertainty and sensitivity analysis for spatial and spectral processing of Pb isotopes in zircon by atom probe tomography

   https://doi.org/10.1002/9781119227250.ch16  

   Blum, TB; Reinhard, DA; Ty, YC; Prosa, J; Larson, DJ; Valley, JW (January 2017, Geography monograph series)

   Moser, DE; Corfu, F; Darling, J; Reddy, SM; Tait, K (Ed.)

   Measuring 207Pb/206Pb ratios by atom probe tomography (APT) has provided new insight into the nanoscale behavior of trace components in zircon, and their relationship to time, temperature and structure. Here, we analyze three APT data sets for a 3.77 Ga zircon from the Beartooth Mountains, USA, and apply systematic ranging approaches to understand the spatial and spectral uncertainties inherent in 207Pb/206Pb analysis by APT. This zircon possesses two, 100% concordant U-Pb analyses by secondary ion mass spectrometry (SIMS), indicative of closed U-Pb systematics on the micron scale since crystallization. APT data sets contain sub-spherical Pb-rich (>0.25% atomic) domains with diameter <15 nm. Broadly consistent Pb-rich regions are defined in applying six different permutations of the two most common cluster identification algorithms. Measured 207Pb/206Pb ratios within Pb-rich domains vary between 0.794±0.15 (±2σ) and 0.715±0.052 depending on the ranging approach, cluster definition protocol and number of clusters interrogated. For the bulk APT data sets, 207Pb/206Pb = 0.353±0.18; this is indistinguishable from the bulk 207Pb/206Pb ratio by SIMS (0.367±0.0037), and statistically distinct from the 207Pb/206Pb ratio within clusters. Bulk and clustered 207Pb/206Pb ratios are consistent with Pb clustering at ~2.8 Ga, during protracted metamorphism and magmatism in the Beartooth Mountains. 10.1002/9781119227250.ch16 

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4. Petrochronologic Constraints on the Timing and Duration of Sill and Dike Emplacement and Associated Contact Metamorphism of Hornfels in the Alta Aureole, Utah, from Zircon and Monazite LA(SS)-ICP-MS

   Bowman, J.R.; Beno, C.J.; Stearns, M.A.; Bartley, J.M.; Fernandez, D.P.; Kylander-Clark, A.C. (January 2022, Transactions American Geophysical Union)

   Two generations of dikes and sills (earlier granodiorite, later leucogranite) have intruded quartzofeldspathic to semi-pelitic hornfels in the innermost ~200 meters of the southern contact aureole of the Alta stock. Both zircon and monazite are present in the older granodiorite intrusions, and monazite alone is present in the younger leucogranite intrusions, and in biotite-rich reaction selvages formed by hydrothermal contact metamorphism in hornfels adjacent to these dikes and sills. U-Pb dates for zircon (n=532) range from ~38 to 32 Ma, with error on individual measurements of ±1–1.5 Ma, and define a KDE peak at 34.5 Ma. These zircon dates are slightly older than, but consistent with, existing zircon data from the Alta stock (35 to 32 Ma; Stearns et al., 2020), suggesting that the construction of the Alta stock began by emplacement of these granodiorite sills and dikes. Monazite Th-Pb dates (n = 888) range from ~41 to 28 Ma with error on individual measurements of ± 1–1.5 Ma. These dates are complicated by disturbances to the U/Th-Pb systematics by common Pb (Pbc) and excess 206Pb due to 230Th. Dates >38 Ma are disturbed by significant Pbc and do not represent crystallization ages. Dates from the granodiorites range from ~38–32 Ma. In individual samples of granodiorite where the disturbance from excess 206Pb can be rigorously evaluated, the monazite data sets yield concordant 232Th-208Pb and 207Pb/206Pb-corrected dates centered at ~35 Ma, consistent with zircon dates from these same samples. Monazite dates from the leucogranites are younger (<33 Ma), consistent with cross-cutting relationships (leucogranites cross-cut granodiorites). The monazite data from the leucogranite sills and dikes do not record magmatic or hydrothermal activity after ~29 Ma, in contrast to the titanite record of hydrothermal activity to as late as ~23 Ma in the border zone of the Alta stock and its endoskarns (Stearns et al., 2020). This absence suggests that once magma injection and associated contact metamorphism in the hornfels ceased, permeability in the hornfels decreased sufficiently by ~29 Ma to prevent subsequent infiltration of significant fluxes of hydrothermal fluid into these hornfels lithologies in the aureole. 

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5. Lead isotopes and rare earth elements geochemistry of global phosphate rocks: Insights into depositional conditions and environmental tracing

   https://doi.org/10.1016/j.chemgeo.2023.121715  

   Wang, Zhen; Hill, Robert; Williams, Gordon; Dwyer, Gary S; Hu, Jun; Schnug, Ewald; Bol, Roland; Sun, Yajie; Coleman, Drew S; Liu, Xiao-Ming; et al (November 2023, Chemical Geology)

   Phosphate rock bears both geologically and environmentally significant information. Rare earth elements and yttrium (i.e., REY) characteristics have been commonly used for reconstructing the redox conditions of depositional environments of and the effects of post-depositional diagenetic alteration on phosphate rock. In addition, phosphate rock is typically enriched in a range of trace elements such as uranium (U) and cadium (Cd) that can be dispersed as contaminants into the environment with phosphate mining and phosphate fertilizer application. Here we report the lead (Pb) isotope compositions combined with Pb and REY concentrations of both global sedimentary and igneous phosphate rocks, aiming to evalute the geological origin of phosphate rocks over time and the potential of using them for environmental tracing. Phopshate rocks samples analyzed in this study were sourced from major economic phosphate deposits in the world, including China, Southern Tethys (e.g., Morocco, Tunisia, Israel), the U.S., India, South Africa and Russia. Our results show a wide range of 208Pb/204Pb (35.70 to 60.58), 207Pb/204Pb (15.20 to 18.25), and 206Pb/204Pb (16.369 to 71.806) ratios in phosphate rocks, with sedimentary phosphate rocks being significantly more radiogenic than igneous rocks. The majority of the sedimentray phosphate rocks show a notable isotopic overprinting by non-radiogenic terrestrial Pb, except for those from Israel and Morocco that have the most radiogenic Pb isotope compositions. Correspondingly, phosphate rocks with more radiogenic Pb isotope ratios show relatively pristine seawater REY features, likely suggesting their preservation of the original oxic seawater conditions and/or minimal diagenetic alteration. In contrast, phosphate rocks with less radiogenic Pb isotope compositions show REY indications for more anoxic seawater redox conditions and/or greater diagenetic alteration. We further evaluate the potential utility of Pb isotopes for tracing the associated contamination with phosphate rock mining and fertilizer application in the environment. In most cases, the radiogenic Pb isotope composition of phosphate rocks and corresponding P-fertilizers is distinctive from both natural crustal Pb and major anthropogenic Pb sources (e.g., Pb ore deposits and pesticides), which provides a great advantage for applying Pb isotopes as environmental tracers for metal(loid) contamination from phosphate sources. The combination of Pb isotope ratios and REY proxies could further constrain the Pb source discrimination. Overall, this study provides new Pb isotopic and REY geochemical data on global phosphate rocks and fertilizers, which lays the groundwork for future regional and local studies on both their geological and environmental implications. 

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