Repeat, fast, and high-resolution mapping of fine-scale trace element distribution in pyrite and marcasite by LA-Q-ICP-MS with the Aerosol Rapid Introduction System (ARIS)
Abstract
The minor and trace element composition of minerals provides critical insights into a variety of geological processes. Multi-element mapping by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is an important technique applied for this purpose and although the method is rapidly advancing, there remains a fundamental compromise between spatial resolution, detection limit, and experiment duration when using sequential mass analyzers. To address the limitation of limited analyte selection for high spatial resolution maps imposed by the sequential nature of typical quadrupole (Q)-ICP-MS, we tested the Aerosol Rapid Introduction System (ARIS) for repeat mapping of the same area. The ARIS is a high-speed transfer tubing system that reduces aerosol washout times, permitting resolution of individual pulses at 40–60 Hz. Here, the ARIS was tested not for pulse resolution but with novel operating conditions optimized to perform fast, high spatial resolution mapping of minor and trace element distribution in pyrite and marcasite. For this purpose, ablation was conducted with a 5 μm beam aperture, a repetition rate of 50 Hz, and a continuous stage scan speed of 40 μm s−1. For each LA-Q-ICP-MS map, data were acquired for six elements with an acquisition time of 20 ms per element. This deliberately reduced the individual pulse resolution of the ARIS but instead exploited the spatial resolution and sensitivity gains afforded by the high-laser repetition rate combined with eficient aerosol transfer. The new method successfully mapped trace elements at single to double-digit parts per million levels, and the maps reveal fine-scale zoning of trace elements with an efective x and y resolution of 5 μm, while white light interferometry showed that for each experiment, only ca. 1 μm of the sample was removed. Repeated mapping of the same area showed excellent correspondence not only between element concentrations in successive experiments but also in the shape, dimension, and location of regions of interest defined by concentration criteria. The very good repeatability of the elemental maps indicates that for studies requiring more analytes, successive mapping of additional elements is possible. By contrast with conventional very small spot (i.e., 5 μm) analysis, fast repetition rate and stage scan speed mapping avoids down-hole fractionation efects and minimizes accidental analysis of buried invisible inclusions. Compared to conventional LA-ICP-MS mapping, the method reduces the experiment time by 4–8 times.
Funding statement: Funding for the Anarraaq project was provided by Teck Resources Limited; a Natural Sciences and Engineering Research Council of Canada (NSERC) Collaborative Research Development Grant 452969-13 awarded to Sarah Gleeson, Robert Creaser, and Teck Resources Limited; and an NSERC Vanier Scholarship awarded to Merilie Reynolds. The funding for the LA-ICP-MS study came from a Helmholtz-Rekrutierungsinitive 0316 to Sarah Gleeson. Balz Kamber and Cora McKenna acknowledge support from Science Foundation Ireland (SFI) Grant Number 13/RC/2092, co-funded under the European Regional Development Fund.
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Articles in the same Issue
- MSA Review
- Nickel in olivine as an exploration indicator for magmatic Ni-Cu sulfide deposits: A data review and re-evaluation
- Repeat, fast, and high-resolution mapping of fine-scale trace element distribution in pyrite and marcasite by LA-Q-ICP-MS with the Aerosol Rapid Introduction System (ARIS)
- Continuous Be mineralization from two-mica granite to pegmatite: Critical element enrichment processes in a Himalayan leucogranite pluton
- An evolutionary system of mineralogy, Part VI: Earth’s earliest Hadean crust (>4370 Ma)
- Oxidation or cation re-arrangement? Distinct behavior of riebeckite at high temperature
- Fe3+/FeT ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy
- How clay delamination supports aseismic slip
- The influence of Al2O3 on the structural properties of MgSiO3 akimotoite
- Atomistic insight into the ferroelastic post-stishovite transition by high-pressure single-crystal X-ray diffraction
- Epidote as a conveyor of water into the Earth’s deep mantle in subduction zones: Insights from coupled high-pressure and high-temperature experiments
- Potential link between antigorite dehydration and shallow intermediate-depth earthquakes in hot subduction zones
- Stability of Fe5O6 and its relation to other Fe-Mg-oxides at high pressures and temperatures
- From schwertmannite to natrojarosite: Long-term stability and kinetic approach
- Trace element and isotopic (S, Pb) constraints on the formation of the giant Chalukou porphyry Mo deposit, NE China
- Textural and chemical evolution of magnetite from the Paleozoic Shuanglong Fe-Cu deposit: Implications for tracing ore-forming fluids
- Jingwenite-(Y) from the Yushui Cu deposit, South China: The first occurrence of a V-HREE-bearing silicate mineral
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- Evaluating the physicochemical conditions for gold occurrences in pyrite
- Letter
- Synthesis and structural analysis of CaFe2O4-type single crystals in the NaAlSiO4-MgAl2O4-Fe3O4 system
Articles in the same Issue
- MSA Review
- Nickel in olivine as an exploration indicator for magmatic Ni-Cu sulfide deposits: A data review and re-evaluation
- Repeat, fast, and high-resolution mapping of fine-scale trace element distribution in pyrite and marcasite by LA-Q-ICP-MS with the Aerosol Rapid Introduction System (ARIS)
- Continuous Be mineralization from two-mica granite to pegmatite: Critical element enrichment processes in a Himalayan leucogranite pluton
- An evolutionary system of mineralogy, Part VI: Earth’s earliest Hadean crust (>4370 Ma)
- Oxidation or cation re-arrangement? Distinct behavior of riebeckite at high temperature
- Fe3+/FeT ratios of amphiboles determined by high spatial resolution single-crystal synchrotron Mössbauer spectroscopy
- How clay delamination supports aseismic slip
- The influence of Al2O3 on the structural properties of MgSiO3 akimotoite
- Atomistic insight into the ferroelastic post-stishovite transition by high-pressure single-crystal X-ray diffraction
- Epidote as a conveyor of water into the Earth’s deep mantle in subduction zones: Insights from coupled high-pressure and high-temperature experiments
- Potential link between antigorite dehydration and shallow intermediate-depth earthquakes in hot subduction zones
- Stability of Fe5O6 and its relation to other Fe-Mg-oxides at high pressures and temperatures
- From schwertmannite to natrojarosite: Long-term stability and kinetic approach
- Trace element and isotopic (S, Pb) constraints on the formation of the giant Chalukou porphyry Mo deposit, NE China
- Textural and chemical evolution of magnetite from the Paleozoic Shuanglong Fe-Cu deposit: Implications for tracing ore-forming fluids
- Jingwenite-(Y) from the Yushui Cu deposit, South China: The first occurrence of a V-HREE-bearing silicate mineral
- Wenjiite, Ti10(Si,P,◻)7, and kangjinlaite, Ti11(Si,P)10, new minerals in the ternary Ti-P-Si system from the Luobusa ophiolite, Tibet, China
- Evaluating the physicochemical conditions for gold occurrences in pyrite
- Letter
- Synthesis and structural analysis of CaFe2O4-type single crystals in the NaAlSiO4-MgAl2O4-Fe3O4 system