Correlated Multi-Technique Characterisation of Sulfur-Bearing Serpentine in Carbonaceous Chondrites

Phyllosilicate minerals in the carbonaceous chondrites provide insights into processes in primitive parent bodies of the early Solar System. It is widely agreed that the CM- and CI-type carbonaceous chondrites underwent aqueous alteration on their parent bodies, resulting in phyllosilicate-rich matrices, where the dominant mineral phase is serpentine. There are many previous studies investigating phyllosilicate structure in carbonaceous chondrites, however, the presence of sulfur in these minerals and its effect on crystal lattice structure has not been studied in detail. We are investigating how the presence of sulfur (up to ≃9-10 wt% SO₃) in serpentine phyllosilicate regions effects basal lattice spacing measurements of serpentine-like minerals in CM- and CI-type chondritic and related asteroidal material.

Four specimens are being studied for this work: Winchcombe and Aguas Zarcas (CM-type), and Ryugu samples (A0058-C2001-08, A0104-00200502 and A0104-01700602) from Hayabusa2 and Ivuna (CI-type). All samples are TEM wafers. We have used a multi-technique approach to study the samples, with the E01 JEOL ARM200CF and E02 JEOL ARM300CF electron microscopes at the ePSIC facility at Diamond Light Source in Harwell, UK. EDS compositional data has been collected using the E01 microscope, whilst HRTEM and HAADF imaging data has been collected at E02. At E02 we are also applying a new 4D-STEM nano-diffraction technique in order to collect lattice spacing data to correlate with our other HRTEM results. Fe-K XANES analyses on Winchcombe and Ryugu have been carried out using the I18 microprobe and I14 hard x-ray nanoprobe respectively, also at Diamond Light Source, to constrain Fe³⁺/ΣFe. By combining these techniques we aim to better understand the physical and chemical structure of serpentine-like minerals in carbonaceous chondrites.

Initial analyses have shown that sulfur presence in carbonaceous chondrite phyllosilicates reduces the basal lattice spacings of serpentine-like minerals. In these sulfur-bearing regions, we have been finding lattice spacings in the range ~0.60-0.74nm for the CM-type chondrites. For the CI-type, these range between ~0.65-0.76nm. Differences in the reduced lattice spacing ranges are likely related to the redox state of the sulfur. In Ryugu and other carbonaceous chondrites the sulfur appears reduced; its content in serpentine is low and we see FeS grains. Comparatively, in Winchcombe (and others) more of the sulfur seems to be in the serpentine structure.

We can conclude that in serpentine-like minerals, the presence of sulfur appears to reduce basal lattice spacing values compared to the expected d-spacing value of 0.70nm for serpentine. Possible reasons for this include further investigations into the valency of the sulfur ions, the bonding environment within serpentine layers, and the location of sulfur in either the octa- or tetrahedral lattice sites.