Zircon U-Pb, and garnet Sm-Nd and Lu-Hf dates provide important constraints on local and orogenic scale processes in lower-crustal rocks. However, in high-temperature metamorphic rocks these isotopic systems typically yield significant ranges reflecting both igneous and metamorphic processes. Therefore, linking dates to specific aspects of rock history can be problematic. In Fiordland, New Zealand, granulite-facies orthogneiss is cut by leucosomes that are bordered by garnet clinopyroxene reaction zones (garnet reaction zones). In both host orthogneiss and garnet reaction zones, zircon are typically anhedral with U-Pb dates ranging from 118.30 ± 0.13 to 115.70 ± 0.18 Ma (CA-ID-TIMS) and 121.4 ± 2.0 to 109.8 ± 1.8 Ma (SHRIMP-RG). Zircon dates in host and garnet reaction zone do not define distinct populations. In addition, the dates cannot be readily grouped based on external morphology or internal CL zoning. Zircon trace-element concentrations indicate two distinct crystallization trends, clearly seen in Th and U. Garnet occurs in selvages to the leucosome veins and in the adjacent garnet reaction zones. In selvages and host orthogneiss, garnet is generally 0.5 to 1 cm diameter and euhedral and is 0.1 to 0.5 cm diameter and subhedral in garnet reaction zones. Garnet Sm-Nd and Lu-Hf dates range from ca. 115 to 101 Ma (including uncertainties) and correlate with grain size. We interpret the CA-ID-TIMS zircon dates to record the age of magma emplacement and the SHRIMP-RG dates to record a range from igneous crystallization to metamorphic dissolution and reprecipitation and/or local Pb loss. Zircon compositional trends within the garnet reaction zone and host are compatible with locally isolated melt and/or separate intrusive magma batches for the two samples described here. Dates for the largest, ~1 cm, garnet of ~113 Ma record growth during metamorphism, while the smaller grains with younger dates reflect high-temperature intracrystalline diffusion and isotopic closure during cooling. The comprehensive geochronological data set for a single location in the Malaspina Pluton illustrates a complex and protracted geologic history common in granulite facies rocks, estimates lower crustal cooling rates of ~20 °C/m.y., and underlines the importance of multiple chronometers and careful textural characterization for assigning meaningful ages to lower-crustal rocks. Numerous data sets from single locations, like the one described here, are needed to evaluate the spatial extent and variation of cooling rates for Fiordland and other lower crustal exposures.
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Chemical abrasion: the mechanics of zircon dissolution
Abstract. Chemical abrasion is a technique that combines thermal annealing and partialdissolution in hydrofluoric acid (HF) to selectively removeradiation-damaged portions of zircon crystals prior to U–Pb isotopicanalysis, and it is applied ubiquitously to zircon prior to U–Pb isotopedilution thermal ionization mass spectrometry (ID-TIMS). The mechanics ofzircon dissolution in HF and the impact of different leaching conditions onthe zircon structure, however, are poorly resolved. We present amicrostructural investigation that integrates microscale X-ray computedtomography (µCT), scanning electron microscopy, and Ramanspectroscopy to evaluate zircon dissolution in HF. We show that µCTis an effective tool for imaging metamictization and complex dissolutionnetworks in three dimensions. Acid frequently reaches crystal interiors viafractures spatially associated with radiation damage zoning and inclusionsto dissolve soluble high-U zones, some inclusions, and material aroundfractures, leaving behind a more crystalline zircon residue. Other acid pathsto crystal cores include the dissolution of surface-reaching inclusions andthe percolation of acid across zones with high defect densities. In highlycrystalline samples dissolution is crystallographically controlled withdissolution proceeding almost exclusively along the c axis. Increasing theleaching temperature from 180 to 210 ∘C results indeeper etching textures, wider acid paths, more complex internal dissolutionnetworks, and greater volume losses. How a grain dissolves strongly dependson its initial radiation damage content and defect distribution as well asthe size and position of inclusions. As such, the effectiveness of anychemical abrasion protocol for ID-TIMS U–Pb geochronology is likelysample-dependent. We also briefly discuss the implications of our findingsfor deep-time (U-Th)/He thermochronology.
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- Award ID(s):
- 2223808
- NSF-PAR ID:
- 10425052
- Date Published:
- Journal Name:
- Geochronology
- Volume:
- 5
- Issue:
- 1
- ISSN:
- 2628-3719
- Page Range / eLocation ID:
- 127 to 151
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract. The loss of radiogenic Pb from zircon is known to be a major factor that can cause inaccuracy in the U–Pb geochronological system; hence, there is a need to better characterize the distribution of Pb loss in natural samples. Treatment of zircon by chemical abrasion (CA) has become standard practice in isotope dilution–thermal ionization mass spectrometry (ID-TIMS), but CA is much less commonly employed prior to in situ analysis via laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS) or secondary ionization mass spectrometry (SIMS). Differentiating the effects of low levels of Pb loss in Phanerozoic zircon with relatively low-precision in situ U–Pb dates, where the degree of Pb loss is insufficient to cause discernible discordance, is challenging. We show that U–Pb isotopic ratios that have been perturbed by Pb loss may be modeled by convolving a Gaussian distribution that represents random variations from the true isotopic value stemming from analytical uncertainty with a distribution that characterizes Pb loss. We apply this mathematical framework to model the distribution of apparent Pb loss in 10 igneous samples that have both non-CA LA-ICP-MS or SIMS U–Pb dates and an estimate of the crystallization age, either through CA U–Pb or 40Ar/39Ar geochronology. All but one sample showed negative age offsets that were unlikely to have been drawn from an unperturbed U–Pb date distribution. Modeling apparent Pb loss using the logit–normal distribution produced good fits with all 10 samples and showed two contrasting patterns in apparent Pb loss; samples where most zircon U–Pb dates undergo a bulk shift and samples where most zircon U–Pb dates exhibited a low age offset but fewer dates had more significant offset. Our modeling framework allows comparison of relative degrees of apparent Pb loss between samples of different age, with the first and second Wasserstein distances providing useful estimates of the total magnitude of apparent Pb loss. Given that the large majority of in situ U–Pb dates are acquired without the CA treatment, this study highlights a pressing need for improved characterization of apparent Pb-loss distributions in natural samples to aid in interpreting non-CA in situ U–Pb data and to guide future data collection strategies.
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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.more » « less
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Interpretation of geochronological and petrological data from partially-melted granulite is challenging. However, integration of multiple chronometers and mineral assemblage diagrams (MAD) can be used to estimate the nature and duration of processes. Excellent lower-crustal exposures of garnet granulite from the Malaspina Pluton, Fiordland New Zealand provide an ideal place to employ this kitchen sink approach. We use zircon U-Pb ages from LA-ICPMS, SHRIMP-RG, and CA-TIMS, garnet Lu-Hf and Sm-Nd ages, and MAD in order to evaluate local partial melting vs. melt injection, equilibrium volumes, P-T conditions, and the duration of lower crustal thermal events. Host diorite (H), garnet-clinopyroxene reaction zones (GRZ), coarse garnet selvages, and tonalite veins provide a record of intrusion and granulite facies partial melting. Zircon U-Pb ages range from 123 to 107 Ma (all); LA-ICPMS ages contain the entire range; CA-TIMS ages range from 118.30±0.13 to 115.7±0.18 Ma; and SHRIMP-RG ages range from 121.4±2 to 109.8±1.8 Ma. The latter two techniques are interpreted to indicate primary igneous crystallization from ~119 to ~116 Ma and the youngest ~110 Ma ages are interpreted as metamorphic zircon growth. Garnet ages for ~1 cm grains are ~113 Ma (Lu-Hf & Sm-Nd) and record metamorphic growth, and <0.3 mm grains with Sm-Nd ages from 113 to 104 Ma reflect high temperature intracrystalline diffusion and isotopic closure during cooling to amphibolite facies. Zircon trace-element compositions indicate 2 distinct crystallization trends reflecting evolution of primary magma batches. MAD indicate that garnet was not in equilibrium with sampled rock compositions. Instead, garnet shows apparent equilibrium with a modeled mixture of the GRZ and the H and grew in equilibrium with an effective bulk composition that shifted toward the leucosome. This would produce the observed increase in garnet grossular content. We conclude that: Malaspina rocks from Crooked Arm preserve evidence for 2 igneous layers which evolved as discrete magmas, igneous crystallization lasted 2 to 3 m.y., granulite metamorphism peaked ~ 3 m.y. after intrusion, metamorphism lasted ≥3 m.y., cooling occurred at ~20°C/m.y., and granulite minerals equilibrated with a mixture of solid phases and melt at ~14 kbar and 920°C (based on garnet compositions and MAD).more » « less
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null (Ed.)Abstract The response of sediment routing to climatic changes across icehouse-to-greenhouse turnovers is not well documented in Earth's pre-Cenozoic sedimentary record. Southwest Gondwana hosts one of the thickest and most laterally extensive records of Earth's penultimate icehouse, the late Paleozoic ice age. We present the first high-resolution U-Pb zircon chemical abrasion–isotope dilution–thermal ionization mass spectrometry (CA-ID-TIMS) analysis of late Paleozoic ice age deposits in the Kalahari Basin of southern Africa, which, coupled with existing CA-ID-TIMS zircon records from the Paraná and Karoo Basins, we used to refine the late Paleozoic ice age glacial history of SW Gondwana. Key findings from this work suggest that subglacial evidence in the Kalahari region is restricted to the Carboniferous (older than 300 Ma), with glacially influenced deposits culminating in this region by the earliest Permian (296 Ma). The U-Pb detrital zircon geochronologic records from the Paraná Basin of South America, which was located downstream of the Kalahari Basin in the latest Carboniferous and Permian, indicate that large-scale changes in sediment supplied to the Paraná were contemporaneous with shifts in the SW Gondwana ice record. Gondwanan deglaciation events were associated with the delivery of far-field, African-sourced sediments into the Paraná Basin. In contrast, Gondwanan glacial periods were associated with the restriction of African-sourced sediments into the basin. We interpret the influx of far-field sediments into the Paraná Basin as an expansion of the catchment area for the Paraná Basin during the deglaciation events, which occurred in the latest Carboniferous (300–299 Ma), early Permian (296 Ma), and late early Permian (<284 Ma). The coupled ice and detrital zircon records for this region of Gondwana present opportunities to investigate climate feedbacks associated with changes in freshwater and nutrient delivery to late Paleozoic ocean basins across the turnover from icehouse to greenhouse conditions.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.5194/gchron-5-127-2023
