Microstructure of 24-1928 Ma concordant monazites; implications for geochronology and nuclear waste deposits

The microstructure of monazite was studied using scanning electron microscopy (SEM), electron microprobe analysis (EMP), X-ray diffraction patterns (XRD), and transmission electron microscopy (TEM). Four well-characterized monazites were investigated, having very different concordant U-Pb ages (24 to 1928 Ma), and up to ∼15 wt.% ThO₂, and ∼0.94 wt. % UO₂. The SEM and EMP analyses of polished single crystal fragments reveal the absence of significant chemical zoning. XRD and TEM investigations show that the monazites are not metamict, despite their old ages, very high abundances of radionuclides, and hence, high time-integrated radiation doses. Except for the youngest one, the monazite crystals are composed of a mosaic of crystalline but slightly distorted domains. This structure is responsible for the presence of (1) mottled diffraction contrasts on the TEM, and (2) a second structural phase (B), with very broad reflections in the XRD patterns. Older monazites receive higher self-irradiation doses, and hence, they contain higher amounts of this B-phase. For the 1928 Ma monazite, XRD reveals only the broad reflections of phase B, implying that the whole monazite was affected by radiation damage that resulted in total distortion of the lattice. It is concluded that radiation damage in the form of amorphous domains does not accumulate in monazite because self-annealing heals the defects as they are produced by α-decay damage. The only memory of irradiation-induced defects is the presence of distorted domains. As the diffusion rate of Pb in an undisturbed monazite lattice is extremely low, Pb loss due to volume diffusion out of the monazite lattice is virtually impossible. This is considered as one reason why almost all monazites have concordant U-Th-Pb ages. Moreover, as long-term self-irradiation effects are limited in monazite, we consider this phase as a good candidate for the storage of high-level nuclear waste under the aspect of its high resistance to irradiation.     

Decoding a protracted zircon geochronological record in ultrahigh temperature granulite,and persistence of partial melting in the crust,Rogaland, Norway

This contribution evaluates the relation between protracted zircon geochronological signal and protracted crustal melting in the course of polyphase high to ultrahigh temperature (UHT; T?>?900 °C) granulite facies metamorphism. New U–Pb, oxygen isotope, trace element, ion imaging and cathodoluminescence (CL) imaging data in zircon are reported from five samples from Rogaland, South Norway. The data reveal that the spread of apparent age captured by zircon, between 1040 and 930 Ma, results both from open-system growth and closed-system post-crystallization disturbance. Post-crystallization disturbance is evidenced by inverse age zoning induced by solid-state recrystallization of metamict cores that received an alpha dose above 35 × 10¹⁷ α  g^?1. Zircon neocrystallization is documented by CL-dark domains displaying O isotope open-system behaviour. In UHT samples, O isotopic ratios are homogenous (δ¹⁸O = 8.91?±?0.08‰), pointing to high-temperature diffusion. Scanning ion imaging of these CL-dark domains did not reveal unsupported radiogenic Pb. The continuous geochronological signal retrieved from the CL-dark zircon in UHT samples is similar to that of monazite for the two recognized metamorphic phases (M1: 1040–990 Ma; M2: 940–930 Ma). A specific zircon-forming event is identified in the orthopyroxene and UHT zone with a probability peak at ca. 975 Ma, lasting until ca. 955 Ma. Coupling U–Pb geochronology and Ti-in-zircon thermometry provides firm evidence of protracted melting lasting up to 110 My (1040–930 Ma) in the UHT zone, 85 My (ca. 1040–955 Ma) in the orthopyroxene zone and some 40 My (ca. 1040–1000 Ma) in the regional basement. These results demonstrate the persistence of melt over long timescales in the crust, punctuated by two UHT incursions.     

An XRD, TEM and Raman study of experimentally annealed natural monazite

 The healing of radiation damage in natural monazite has been experimentally studied in annealing experiments using XRD, TEM, Raman microprobe and cathodoluminescence analysis. The starting material was a chemically homogeneous monazite from a Brazilian pegmatite with a concordant U–Pb age of 474 ± 1 Ma and a U–Th/He age of 479 Ma. The monazite shows nm-scale defects induced by radioactive decay. The X-ray pattern of the unheated starting material revealed two distinct monazite “phases” A and B with slightly different lattice parameters. Monazite A shows sharp reflections of high amplitudes and slightly expanded lattice parameters (1% in volume) compared to a standard monazite. Phase B exhibits very broad reflections of low amplitudes. Two sets of experiments were performed. First, dry monazite powder was annealed at 500, 800 and 1000 °C for 7 days. Each run product was analysed by X-ray diffractometry. Second, monazite grains were hydrothermally annealed at temperatures from 500 to 1200 °C for 5 to 15 days. TEM observations show that partial healing of the monazite lattice already occurred at 500 °C and increased gradually with temperature, so that after 10 days at 900 °C complete healing was achieved. The observations are interpreted accordingly: the starting material has a mosaic structure consisting of two domains, A and B, which are basically two monazite crystals with different lattice parameters. We suggest that the A domains correspond to well-crystallised areas where helium atoms are trapped. The accumulation of He causes expansion of the A monazite lattice. Diffraction domains B are interpreted as a helium-free distorted monazite crystal lattice, which can be referred to old alpha-recoil tracks. These B domains are composed of “islands” with an expanded lattice, induced by the presence of interstitials, and “islands” of a compressed monazite lattice, induced by presence of vacancies. Both the islands will pose stress on the lattice in the vicinity of the islands. The broadening of the B reflections is due to the expanded or compressed diffraction domains and to the different amount of the distortion. With increasing temperature the unit-cell volume of monazite A decreases, i.e. the position of the A reflections shifts towards smaller d _hkl values. This was interpreted as a relaxation of the monazite lattice due to helium diffusion out of the monazite lattice. Simultaneously, the nm-sized defect domains B are healed. At 900–1000 °C only a monazite with well-crystallised lattice and minimum unit-cell volume is observed. Received: 7 May 2001 / Accepted: 11 October 2001     

Nanoscale resetting of the Th/Pb system in an isotopically-closed monazite grain: A combined atom probe and transmission electron microscopy study

Understanding the mechanisms of parent-daughter isotopic mobility at the nanoscale is key to rigorous interpretation of Ue The Pb data and associated dating. Until now, all nanoscale geochronological studies on geological samples have relied on either Transmission Electron Microscope(TEM) or Atom Probe Microscopy(APM) characterizations alone, thus suffering from the respective weaknesses of each technique. Here we focus on monazite crystals from a ~1 Ga, ultrahigh temperature granulite from Rogaland(Norway). This sample has recorded concordant UeP b dates(measured by LA-ICP-MS) that range over 100 My, with the three domains yielding distinct isotopic Ue Pb ages of 1034 ± 6 Ma(D1; Srich core), 1005 ± 7 Ma(D2), and 935 ± 7 Ma(D3), respectively. Combined APM and TEM characterization of these monazite crystals reveal phase separation that led to the isolation of two different radiogenic Pb(Pb*) reservoirs at the nanoscale. The S-rich core of these monazite crystals contains Cae Srich clusters, 5 -10 nm in size, homogenously distributed within the monazite matrix with a mean interparticle distance of 40 -60 nm. The clusters acted as a sink for radiogenic Pb(Pb*) produced in the monazite matrix, which was reset at the nanoscale via Pb diffusion while the grain remained closed at the micro-scale. Compared to the concordant ages given by conventional micro-scale dating of the grain,the apparent nano-scale age of the monazite matrix in between clusters is about 100 Myr younger, which compares remarkably well to the duration of the metamorphic event. This study highlights the capabilities of combined APM-TEM nano-structural and nano-isotopic characterizations in dating and timing of geological events, allowing the detection of processes untraceable with conventional dating methods.