CMCA TECHNOLOGY DEVELOPMENT AND INSTRUMENTATION

The University of Western Australia’s Centre for Microscopy, Characterisation and Analysis (CMCA) is a $40M core facility providing analytical solutions across a diverse array of scientific research.  The world-class facilities and associated technical and academic expertise are the focus of micro-analytical and characterisation activities within Western Australia, while strong links and collaborations have earned the CMCA an excellent national and international reputation.  The CMCA incorporates the Western Australian Centre for Microscopy, and is a node of the NCRIS Characterisation capabilities, the National Imaging Facility (NIF) and the Australian Microscopy and Microanalysis Research Facility (AMMRF).  It is also associated with the NCRIS funded Australian National Fabrication Facility (ANFF), and AuScope, which have made a substantial contribution to facilities run by CMCA.

CMCA capabilities:

•   Secondary Ion Mass Spectrometry (CAMECA IMS 1280 and CAMECA NanoSIMS 50)
•   Electron probe microanalysis (JEOL JXA 8530F)
•   Transmission electron microscopy (FEI Titan, JEOL 2100)
•   Scanning electron microscopy (FEI Verios XHR, Zeiss 1555, Tescan Vega3)
•   X-ray powder diffraction (Panalytical Empyrean)
•   X-ray micro-CT (Xradia)
•   Confocal Raman imaging with AFM (WiTec Alpha 300RA+)
•   NMR spectroscopy (2 Bruker Avance and 2 Varian spectrometers)
•   X-ray crystallography (Oxford Diffraction)
•   GC and HPLC mass spectrometry
•   Bioimaging, flow cytometry, cell sorting, and laser micro-dissection
•   Optical and confocal microscopy
•   Biological sample cryo-preparation and ultramicrotomy
   

THE AMMRF FLAGSHIP ION PROBE FACILITY

The CAMECA IMS 1280 and NanoSIMS 50 are flagship instruments of the AMMRF.  The AMMRF Flagship Ion Probe Facility offers state-of-the-art secondary ion mass spectrometry (SIMS) capabilities to the Australian and international research communities, allowing in situ, high-precision isotopic and elemental analyses, and secondary ion imaging on a wide range of samples.

The IMS 1280 large-geometry ion probe, installed in 2009, was co-funded by the University, the State Government of Western Australia, and the Federal Government’s Department of Innovation, Industry, Science and Research (DIISR) under the ‘Characterisation’ (AMMRF) and ‘Structure and Evolution of the Australian Continent’ (AuScope) capabilities of the National Collaborative Research Infrastructure Strategy (NCRIS).  The NanoSIMS 50, installed in 2003, was funded through the Federal Government’s NCRIS-precursor, the Major National Research Facility scheme (NANO-MNRF).

The Ion Probe Facility is a key characterisation component within the ARC Centre of Excellence for Core to Crust Fluid Systems.  To ensure the highest levels of quality and throughput, the CCFS has provided funding for a Research Associate position within the Ion Probe Facility, to facilitate direct scientific and technical interaction for all CCFS users and projects.

The Ion Probe Facility is also a member of the International Atomic Energy Agency’s (IAEA) Network of Analytical Laboratories (NWAL), performing U isotope analyses on environmental dust particles for Nuclear Safeguards.

PROGRESS IN 2014:

Recent successes in ARC LIEF funding have updated the electron microscopy facilities at CMCA, with the installation in 2014 of a FEI Titan TEM, a FEI Verios XHR high resolution SEM, and Confocal Raman with AFM.  Further success in the 2014 LIEF round will see the installation in 2015-16 of a Focused Ion Beam (FIB) platform for the preparation of TEM, NanoSIMS and atom probe samples.

The CMCA has also received funding for a new Cameca NanoSIMS 50L ion probe through CSIRO’s Science and Industry Endowment Fund (SIEF) via the National Resources Science Precinct (NRSP).  The new instrument will be part of the tripartite Advanced Resources Characterisation Facility, along with a Cameca LEAP4000 Atom Probe to be located at Curtin University, and the in-house development of a MAIA mapping facility at CSIRO.  The NanoSIMS 50L represents a considerable technological advance over the existing NanoSIMS, with a seven-FC/EM multicollector array and a new oxygen ion source allowing high-resolution isotope measurements on geological samples.

In 2014, the Ion Probe Facility has continued to contribute to various projects in the context of CCFS.  These have included a wide range of topics, from the magmatic processes and crustal growth, the origin of ore deposits (O isotopes in zircon, E. Belousova and Y. Lu; S isotopes in sulfides, M. Fiorentini) and the exploration of redox processes in the deep Earth (Si and C isotopes in moissanite; J. Huang and W. Griffin).  In addition, the NanoSIMS has also been involved in the measurement of element diffusion across mineral interfaces, trace element transportation along grain boundaries, and S isotopes (D. Wacey, M. Fiorentini).

High-precision isotope measurement with SIMS requires calibration against known standards to correct for instrumental mass fractionation between analysis sessions.  This varies significantly between different materials, such that each new material analysed by SIMS necessitates the development of new standards.  Standards are in constant development at CMCA and currently include pyroxene and olivine (O isotopes) as well as a range of Si-bearing materials (SiC, Si metal, silicates) for Si isotopes.  Development continues on diamond (C isotopes), lawsonite, pyroxene, garnet and olivine (O isotopes), tourmaline and serpentine (B isotopes), pentlandite, pyrrhotite and chalcopyrite (S and Fe isotopes).  The development of standards for unknown isotope systems aims to identify potential new geochemical tools.

CMCA RESEARCH HIGHLIGHTS:

Once again the Ion Probe Facility at CMCA was highly productive during 2014, contributing to a number of projects across the whole CCFS.  Highlights include:

Zircon analysis

Zircon is a robust mineral whose chemical and isotopic composition has the ability to preserve information about its growth environment.  The analysis of oxygen isotope in zircon is thus a powerful tool to identify the magmatic origin of these crystals.  E. Belousova and co-authors have conducted an integrated isotopic (U-Pb, Hf and O) study of zircon crystals from upper-mantle rocks from the Tumut ophiolite complex.  Their study shows that crustally-derived zircons can be introduced into mantle rocks even after their obduction onto the continental crust, thus proposing an alternative explanation for the presence of this mineral in ultramafic rocks from ophiolite complexes.  This work has been published in the journal Geology [Belousova, E., Gonzáles-Jiménez J.-M., Graham I., Griffin, William L., O’Reilly S.Y., Pearson N., Martin L., Craven S., Talavera C. (2015).  The enigma of crustal zircons in upper-mantle rocks: Clues from the Tumut ophiolite, southeast Australia. Geology, vol. 43, p. 119-122].

Sulfur isotope analysis

The ability to measure all 4 stable sulfur isotopes in sulfide minerals in situ, makes the CAMECA IMS1280 one of the most powerful techniques available for S isotope analysis.  During 2014, the IMS1280 was used to analyse several sets of Precambrian sulfides in order to determine sulfur sources in deep time.  One project, led by CCFS SAC member James Farquhar at the University of Maryland, measured S isotopes in 2.5 billion year old carbonate rocks from Brazil to investigate S sources in the Neoarchean ocean.  The data revealed that bacteria were metabolising sulfate even when the ocean contained 1000 times less sulfate than today.  The results were published in the prestigious journal Science (see CCFS publication# 568).

Isotopic Standard development

Due to the strong ‘matrix effect’ inherent in SIMS analysis, each new material requires a chemically (and isotopically) homogeneous standard of known composition with which to calibrate the instrument.  In addition, the testing of new standards extends our capabilities into hitherto unexplored isotope systems.  Recent development has included Si isotopes in silicates, SiC and Si metal, C isotopes in SiC, Zr isotopes in zircon crystals from different provenance.  O isotope analysis in garnet is in constant development in order to cover the complex chemistry of this mineral.  The development of a Cr-rich garnet standard is underway in collaboration with J. Huang and aims to provide a better characterisation of mantle-derived garnets.  The combined development of Li and O isotope measurements in olivine and clinopyroxene is also in progress.

Ultra-fine resolution diffusion

The NanoSIMS proved once again that size does matter as a number of projects utilising the ultra-high spatial resolution and sensitivity to determine diffusion profiles across mineral interfaces.  One study, published in Chemical Geology (Saunders et al., Chem. Geol., 364, 20-33), demonstrated how the ability to acquire high-resolution diffusion profiles could be used to better constrain the timing of volcanic processes on the order of days to years.  Similarly, experimental studies on Ni and Co revealed that the activity of SiO₂ has a significant effect on the diffusion rates of these elements in olivine from magmas with different compositions (Zhukova et al., Contrib. Mineral. Petrol., 168, 1029).

 

For further information on JDLC facilities please consult  http://www.cmca.uwa.edu.au/

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JOHN DE LAETER CENTRE 

The John de Laeter Centre (JDLC) is a collaborative research venture involving Curtin University, the University of Western Australia, CSIRO and the Geological Survey of Western Australia.  It hosts over $28M in infrastructure supporting research in: geosciences (geochronology, thermochronology and isotope studies); environmental science; isotope metrology; forensic science; economic geology (minerals and petroleum); marine science; and nuclear science.  Highlights for the 2014 period include:

•   Success in 5 Australian Research Council LIEF proposals resulting in the commissioning of $3,460,000 in high-technology research facilities in 2013 and 2014.
•   National leadership of the AuScope Earth Composition and Evolution program; the award of $800,000 in NCRIS funding to create a laboratory information management system (LIMS) for mineralogical data and a prototype for the national geochemistry community in cooperation with the Australian National Data Service (ANDS).
•   A $12,400,000 Science and Industry Endowment Fund grant will create a collaborative Advanced Resources Characterisation Facility (ARCF) in 2015; JDLC will be responsible for managing the ARCF Geoscience Atom Probe and accessory equipment worth $4,200,000.
•   A major funding agreement with the Chinese Academy of Geological Sciences permitting remote operation of the JDLC Sensitive High Resolution Ion MicroProbe (SHRIMP) from Beijing.
•   The commercialization of JDLC technology was boosted by a four-year R&D agreement with Australian Scientific Instruments (ASI) to advance the commercial potential of the RESOchron laser ablation mass spectrometry instrument platform developed at Curtin, and to develop integrated U-Th-Pb-He geochronology and thermochronology applications.  In 2013, ASI delivered RESOchron systems, based on the JDLC prototype, to labs in China and Canada.
•   High-profile publications, including:
•   the oldest age yet obtained for samples from Mars and the first evidence of the composition of the ancient Martian atmosphere,
•   the oldest age yet obtained for samples from the Apollo Moon missions with implications for understanding the bombardment history of the early Earth,
•   a 200-year climate record for NW Australia obtained from Ningaloo reef corals and a greater understanding of the variability of the Leeuwin warm current,
•   a major study of multiple ice cores confirmed widespread Pb pollution of the Antarctic continent in 1889, almost 22 years before human exploration began.  This date coincides with the onset of base metal smelting activities at Broken Hill and Point Pirie, Australia.
•   A study linking high CO2 contents in the Triassic atmosphere to sea level rise, anoxic oceans and the mass extinction of marine and terrestrial species.

The components of the JDLC are organised into thirteen major facilities.

1.  The Advanced Ultra-Clean Environment (ACE) Facility:  This consists of a ~400m² class 1000 containment space housing four class 10 ultra-clean laboratories, a class 10 reagent preparation laboratory and a −18 °C class 10 cold clean laboratory, located at Curtin University.  The extremely low ultimate particle counts are achieved with successive ‘spaces within spaces’ and HEPA filtration at each stage.

2.  Inductively-Coupled Plasma Mass Spectrometry (ICPMS) Facility:  This facility is located at UWA and consists of:

•   TJA (VG/Fisons) PlasmaQuad 3 Quadrupole ICP-MS.
•   TJA (VG/Fisons) Laserlab high resolution 266 nm (Frequency quadrupled Nd-YAG) laser, capable of the ablation of craters down to 10 μm in diameter.
•   GBC Optimas 8000 Time of Flight ICP-MS
•   Leco Renaissance Time of Flight ICP-MS
•   A wide range of chromatographic and thermal dissociation interfacing is also available.
•    

3.  Argon Isotope Facility:  This is located at Curtin and is equipped with a MAP 215-50 mass spectrometer with a low-blank automated extraction system coupled with a NewWave Nd-YAG dual IR (1064 nm) and UV (216 nm) laser, an electron multiplier detector and Niers source.  Laser analysis allows spatial resolution up to 10 μm for UV laser and 300 μm for IR laser.  Larger sample sizes (>8-10 mg) are accommodated by an automated Pond-Engineering low-blank furnace.  The extraction line has a Nitrogen cryocooler trap and three GP10 getters that allow gas purification.  An Argus VI Mass Spectrometer and a Photon Machines Laser are on order. 

4.  Joint ANU-John de Laeter Centre for Mass Spectrometry (JdLC) Argon Facility:  The new instrument enables work on rare extra-terrestrial sample materials, such as micrometer-size grains recovered from the Itokawa asteroid (see below) by the Japanese spacecraft Hayabusa.
 

5.  A Thermo Argus VI multi-collector noble gas mass spectrometer was installed in November 2012 with funding from a 2012 ARC LIEF grant.  This is a low volume (~700 cc) instrument providing excellent sensitivity and is particularly suited to the isotopic analysis of small samples of the noble gases, and in particular, Argon.  The muticollector design allows simultaneous measurement all five Ar isotopes leading to reduced analysis time and greater productivity.
 

6.  Organic Geochemistry Facility:  This facility is located in Applied Chemistry at Curtin and the instruments used for biomarker, petroleum and water studies include:

•   GCMS (Gas Chromatograph Mass Spectrometer)
•   GC-HRMS-MS (Gas Chromatograph-High Resolution Mass Spectrometer)
•   Py-GC-MS (Pyrolysis-Gas Chromatograph-Mass Spectrometer)
•   LCTOFMS (Liquid Chromatograph-Time of Flight-Mass Spectrometer)
•   LC-MS-MS (Liquid Chromatography-Mass Spectrometry-Mass Spectrometer)
•   HPSEC-DAD (High Performance Size Exclusion Chromatograph-Diode-Array Detection)
•   GCIRMS (Gas Chromatograph-Isotope Ratio-Mass Spectrometer)
•   TD-GC-IRMS (Thermal Desorption-Gas Chromatograph-Isotope Ratio-Mass Spectrometer)
•   EA-IRMS (Elemental Analysis-Isotope Ratio-Mass Spectrometer)

7.  Sensitive High Resolution Ion Micro Probe (SHRIMP):  
The facility at Curtin has two automated SHRIMP II ion microprobes capable of 24-hour operation, together with a preparation laboratory that was remodelled in 2014.  The equipment allows in situ isotopic analysis of chemically complex materials with a spatial resolution of 5-20 microns.  The main application of the SHRIMP instruments at Curtin is for U-Th-Pb geochronology of zircon and other U-bearing minerals, including monazite, xenotime, titanite, allanite, rutile, apatite, baddeleyite, cassiterite, perovskite and uraninite where multiple growth zones commonly require analyses with high spatial resolution.  

8.  Stable Isotope Ratio Mass Spectrometry (SIRMS) Facility:  The West Australian Biogeochemistry Centre (WABC) at UWA is associated with the JdLC.  The WABC currently operates three isotopic ratio mass spectrometers (IRMS) and additional analytical instrumentation (GC, HPLC, CE autoanalyser) for biogeochemical studies.  A fourth IRMS (especially for small-sample δ¹³C and δ¹⁸O and carbonate analysis) is now being commissioned.  The IRMS are coupled with a variety of sample preparation modules to facilitate analysis of a broad range of sample matrices.

 

David Adams (GAU), John Cliff and Matt Kilburn (CMCA) at the June CCFS Research Meeting.

  

9.  Thermal Ionisation Mass Spectrometry (TIMS) Facility:  
The TIMS facility at Curtin incorporates a Thermo Finnegan Triton™ and a VG 354 multicollector mass spectrometer.  The Triton is equipped with a 21-sample turret and 9 faraday cups, enabling a precision of 0.001% on isotopic ratios.  As well as geological applications within the broad field of isotope geochemistry (Re/Os, U/ Pb, Pb/Pb, Sm/Nd, Rb/Sr) the TIMS instruments can be applied to a variety of isotope fingerprinting, such as forensics and the environmental impact of human activities.  The TIMS instruments are also used for the calibration of isotopic standards and the calculation of isotopic abundances and atomic weights.
 

10.  AuScope GeoHistory and (U-Th)/He Facility:  The laboratory at Curtin hosts the prototype of the Alphachron™ automated helium microanalysis instrument now marketed by Australian Scientific Instruments in Canberra.  (U-Th)/He thermochronology involves the measurement of ⁴He generated by the radioactive decay of U and Th in minerals.  The JDLC (U-Th)/He Facility provides thermal-history analysis of metallogenic and petroleum systems by integrating several age-dating capabilities along with 4D thermal modelling.  The Facility is also involved in fundamental collaborative research in the fields of orogenic tectonics, volcanology and quantitative geomorphology.  It now operates a new Alphachron™machine coupled to a RESOlution Excimer laser + Agilent 7700 mass spectrometer.  This “RESOchron” instrument enables the development of in situ U-Pb and (U-Th)/He dating on single crystals of U-bearing minerals and immensely increases the application potential.  In addition, laser-ablation trace element analysis and U-Pb geochronology is now routinely undertaken in this facility, supporting industry, government and University projects.

11.  K-Ar Geochronology Facility:  The K-Ar facility utilises the following instrumentation and techniques:

•   VG3600 noble gas mass spectrometer
•   Heine double vacuum resistance furnace
•   Clay mineral separation laboratory utilising cryogenic disaggregation of rock samples
•   XRD, SEM, TEM, particle size analysis for clay characterisation
•   Vacuum encapsulation station for Ar-Ar dating of ultrafine samples
•   Clays - illite: Dating the timing of diagenetic and deformation events
•   Fault gouge dating (illite) - earthquake and hazard assessment

12.  selFrag Facility:  A new selFrag facility, supported by an ARC LIEF grant, has been installed within the Department of Applied Geology at Curtin University.  The facility provides electric pulse disaggregation for mineral separation, which allows mineral grains to be separated from rock samples without the damage associated with standard crushing techniques.

13. Electron Microscopy Facility (EMF):  The EMF is a new node of the JdLC located at Curtin University; it has three scanning electron microscopes, all with EBSD capability, and a transmission electron microscope, for applications across Earth sciences, materials science, engineering, chemistry and biology.

 

The following is a summary of the capabilities of our major instruments;
 

Zeiss NEON 40 EsB - The Neon is a dual beam focused ion beam scanning electron microscope (FIB-SEM) equipped with a field emission gun and a liquid metal Ga+ ion source.  This instrument combines high resolution imaging with precision ion beam ablation of focused regions which allows for site specific analysis of the surface and subsurface of samples in 2D or 3D.

Key Capabilities

•   High resolution imaging using SE, BSE and inlens detectors (resolution is 1.1 nm at 20 kV to 2.5 nm at 1 kV)
•   Energy Dispersive X-ray Spectroscopy (EDS) point analysis and mapping
•   Electron Backscatter Diffraction (EBSD) mapping, including 3D EBSD
•   Focused Ion Beam (FIB) milling
•   Transmission Electron Microscope (TEM) lamella, Transmission Kikuchi Diffraction (TKD) foil and atom probe tip preparation
•   High resolution 3D tomography 
   

Tescan MIRA3 XMU with Oxford AZTEC EBSD-EDS system

The MIRA is a variable pressure field emission scanning electron microscope (VP-FESEM) equipped with a range of detectors suitable for research in Earth science, forensics, life science and materials science.

Key Capabilities

•   High resolution SE and BSE imaging of 1-3 nm (depending upon conditions used)
•   Fast Electron Backscatter Diffraction (EBSD) mapping
•   Energy Dispersive X-ray Spectroscopy (EDS) point analysis and mapping
•   High quality cathodoluminescence (CL) imaging
•   Electron Beam Induced Current (EBIC) imaging
•   Low vacuum secondary electron imaging up to 500 Pa
•   Scanning Transmission Electron Microscope (STEM) imaging
•   Beam Deceleration Mode (BDM) for low voltage imaging of beam sensitive samples
•   Simultaneous EBSD and EDS mapping
•   Large area autonomous data collection
•   Stereoscopic imaging
  
   

Zeiss EVO

The Zeiss EVO 40XVP is a variable pressure scanning electron microscope (VP-SEM) equipped with a tungsten filament.  The microscope is suitable for general-purpose microstructural analysis at high vacuum, or for the analysis of non-conductive/hydrated samples at lower vacuum.    

Key Capabilities

•   Secondary Electron (SE) imaging
•   Backscattered Electron (BSE) imaging
•   Cathodoluminescence (CL) imaging  
•   Low vacuum secondary electron imaging
•   Energy Dispersive X-ray Spectroscopy (EDS) point analysis and mappingElectron Backscatter Diffraction (EBSD) mapping
  
   

Jeol JEM 2011

The JEM-2011 is a transmission electron microscope (TEM) with a LaB6 filament.  It is equipped with an EDS detector and a scanning transmission electron microscope attachment, allowing for elemental and microstructural analysis at very high magnifications.

Key Capabilities

•   High resolution bright field and dark field imaging
•   Scanning Transmission Electron Microscope (STEM) imaging
•   Selected Area Electron Diffraction (SAED) 
•   Energy Dispersive X-ray Spectroscopy (EDS) analysis