Report for the Joint Use/Research of the Institute for Planetary Materials,
Okayama University
2019 fiscal year first term / second term / others
24/June/2020
Category:

International Joint Research/ General Joint Research/ Joint Use of Facility

Name of the research project: Volcanic Glass
Principal applicant: Matthew Nikitczuk, PhD Candidate, Lehigh University
Affiliated institution and department: Earth and Environmental Sciences Department,
Lehigh University

Collaborator 1
Name: Eizo Nakamura
Affiliated institution and department: Pheasant Memorial Laboratory
Collaborator 2
Name: Tak Kunihiro
Affiliated institution and department: Pheasant Memorial Laboratory
Collaborator 3
Name: Tsutomu Ota
Affiliated institution and department: Pheasant Memorial Laboratory
Collaborator 4
Name: John Mustard
Affiliated institution and department: Department of Earth Environmental and PlanetarySciences, Brown University
Collaborator 5
Name: Ken Williford
Affiliated institution and department: Astrobiogeochemistry Lab, Jet Propulsion Laboratory
Research report: The goal of this visit was to provide overall equal analytical coverage toall four Icelandic and Antarctic hyaloclastite samples of focus and to apply additional in-situ
methods not yet attempted that could feasibly be completed during the 6-week period. Thiswould effectively conclude major analyses at the IPM and mainly entailed completing Table
1 below (light green and red). Some of the analyses listed in the tables below that areimportant to the project but were not performed at the IPM include micro-XRD (performed atWestern University) and ICP-MS/ICP-OES/PGNAA of whole rock and physical separates(performed by Activation Laboratories). In addition to these analyses, nitrogen isotopes of all
samples for this study have been performed at Lehigh University. Figure 1 shows both thetentative workflow that was planned for the execution of desired analyses listed in Table 1 as
well as the actual amended workflow on account of instrument availability/functionality.

Table 1: (Top) Methods applied/planned for hyaloclastites that could have feasibly been completed by the endof October-November 2019 visit to the IPM. (Bottom) Current analytical method completion for volcanic glass
project after October-November 2019 visit to IPM.
As of September 2019 (pre-IPM visit)

As of June 2020 (post-IPM visit)

The following were the task priorities listed in a tentative plan sent to the IPM ahead of theOctober-November-2019 visit. Based on these priorities, a workflow was presented that can beseen in Figure 1A. However, instrument availability and non-functionality prevented this listof tasks to be fully completed and the workflow was amended (see Figure 1B).
1. WDS spot analyses on LAU1 and REY2 using the JEOL JXA-8530 electron probe
microanalyzer. During the previous analyses, running an automated scan resulted in
an offset of up to 10-15 μm between spots chosen for analysis and spots actuallyanalyzed. Remaining WDS spot analyses were therefore to be done manually, one
spot at a time. Upon arrival, LAU1 and REY2 will be ready to immediately be Ccoated and loaded into the instrument.
2. Trace-element spot analyses of suitable phases in Antarctic sections using the IMS5F. KBH17a-2 and CPN2a will be ready for immediate Au-coating and loading intothe instrument.
3. Trace-element spot analyses of suitable phases in Icelandic sections using the IMS5F. Once WDS has been completed on LAU1 and REY2, they can also be preparedfor 5f use. During the previous visit, removal of C-coating was beginning to wear on
the section surfaces. If possible, these sections could be Au-coated either without
removing C or with light removal of C. If this does appear to be a further problem,
spot analyses could be applied to new LAU1 and REY2 sections (2 additional
sections were produced for LAU1, REY2, and CPN2 in April 2019).
4. Additional Raman applied to new LAU1-1, REY2-2 and CPN-2a-2 sections as well as
another KBH17 section, or potentially attempting FTIR. This will mainly be done tofurther locate possible carbonaceous materials.
5. Examine cross-sections of microtubular features for amorphous nano-scalelinings and other elemental depletions at tubule-glass interfaces and/or the interfaces
between possible clay filled micro-dissolution channels and glass and/or smectite
coatings and palagonite/glass as well as the identification of smectite phases withelectron diffraction using the FIB-TEM (JIB-4500 and JEM-2100F). If tasks 1-4 arecompleted in a reasonable time frame and it is possible to apply FIB-TEM, thenkeeping with equal coverage, the goal would be to produce at least one foil from athin section of each of the 4 samples.
6. Possible Li/B/O-isotopes using the Cameca IMS-1280.

(A) Tentative workflow planned for Oct-Nov 2019 IPM visit(B) Actual workflow accounting for instrument availability/functionality

See figure caption below for detailed explanation.

Figure 1 (above): (A) Tentative workflow planned prior to Oct-Nov 2019 IPM visit. (B) Actual amended
workflow that accounted for instrument availability and non-functioning instruments. The circles represent eachof the 2.5 cm diameter round polished thin sections. The numbers represent the planned order of tasks (A) inrelation to task priorities listed on previous page. Colored numbers/arrows represent actual order of operations(B). (1-2) Upon arrival to IPM, the JEOL-JXA-8530 (EPMA) and the JIB-4100/JFM-2100F were unavailable
because other researchers were using the instruments. The IMS-5f was also not operational. Therefore, the firsttask attempted was additional Raman (DXR 532nm) on both newly cut and original thin sections. This work
was performed until the EPMA became available. The original four thin sections were then C-coated, additional
WDS spot analyses were done on the Antarctic samples KBH17a-2 and CPN-2a, and the remaining WDS
coverage of the two Icelandic samples LAU1 and REY2 was completed. In preparation for use of the JIB4100/JFM-2100F and IMS-1280, while the thin sections were in the EPMA, specific spots were chosen andimaged in detail (SEM/BSE/optical). This work was performed until another instrument became available.
When the JIB-4100/JFM-2100F was available and WDS spot analyses were done, it was determined that theJIB-4100/JFM-2100F was not functioning properly and thus could not be used. (3) In preparation for IMS-1280
use, the C-coat was removed (as much as possible without damaging the thin sections) from one thin section
from Iceland and one from Antarctica, sections were then cleaned and Au-coated. Several nitrogen and carbon
maps were attempted but during analyses it became clear that the remaining carbon from the C-coat was asignificant problem and was not being removed by the pre-sputtering stage. Therefore, it was decided that thenew thin sections which had never been C-coated were needed for this analysis. (4) Four of the newly cut thinsections were cleaned and Au-coated then put directly into the JSM 7001F (SEM) to choose new locations ofinterest and capture SEM/BSE images of those locations. (5) Newly SEM-imaged and Au-coated thin sections
were inserted into the IMS-1280 to re-attempt N-C mapping. A total of three maps for each of the four thinsections was produced. (6) Post-SIMS mapping BSE images of the new thin sections were then captured using
the JSM 7001F.

Summary1. Complete WDS coverage of the four Icelandic and Antarctic hyaloclastites wascompleted.
2. Some additional Raman analyses were performed but largely unsuccessful indetecting organic carbonaceous material in relation to alteration textures. Thin section
epoxy appeared to be a problem, but previous attempts even on cut rock slabs werealso unsuccessful in detecting organic carbon. However, several secondary phases
were confirmed using this method. No FTIR was attempted.
3. Several N-C maps were collected for each of the four samples using new thinsections. Even without having been C-coated, it still appears that sample preparation
is an issue and that thin section epoxy may also still be a problem. Several maps arelikely not usable for this reason as well as possible non-orthogonal orientations (withrespect to ion beam) of thin section surfaces during mapping. Second opinions on NC map quality are likely required (see N-C SIMS Examples below and the November
29 SIMS report “Distribution of carbonaceous materials in Murchison and Martian
analogous rocks”)
4. No FIB-TEM analyses were able to be completed.
5. No SIMS trace element spot analyses were able to be completed.
6. Although several tasks were unable to be completed, this visit has concluded major
analytical runs during long term visits to the IPM. The range of data collected issubstantial and in addition to the analyses performed at the IPM and labs outside of
Lehigh University, there is a significant nitrogen content and isotope data set(collected at Lehigh University) that bolsters the overall data. The data are currently
being used to produce a manuscript. See pages 7-8 below for some examples oftentative figures to be included the manuscript.

N-C SIMS Examples

The above two nitrogen and carbon maps produced using the IMS-1280 show large variations
in nitrogen particularly. The map sizes are 80 μm2, which is comparable to the size of theplug in the instrument. What especially stands out in the map on the right is that the patch offresh volcanic glass in the center of the map shows a large difference in N content from thelower to upper portions. Essentially, one half contains more than the other half. Suchvariations may be due to variations in the orientation of the plug itself, the beam orientation
with respect to the surface and not necessarily the sample/phases present. Therefore, maps
exhibiting these variations may not be usable.

The above two N-C SIMS maps demonstrate that topographic lows (fractures, cleavage,phase boundaries) within thin sections are locations where N, C and Cl highs are detected.
The correlation with Cl suggests that the N and C are likely associated with epoxy resin usedin the production of the thin section and thus are not significant finds. However, as the above
two maps show, there are locations that show virtually no nitrogen (e.g., apophyllite at centerof map on left, zeolite at top right of map on right) is detected and thus not insignificant
positive detections. Could maps such as these be more useful in determining where N is notrather than where it is? These two maps are tentative figures to be included in the current
manuscript in preparation.

Examples of tentative figures to be included in current manuscript in preparation

Major volcanic rock chemical classifications of glass shards (EPMA data collected at IPM) and whole rock
(ICPOES/ICPMS/XRF from Activation Labs and IPM) hyaloclastites collected from Iceland, Antarctica(Kirkpatrick Basalts) and Fort Rock, Oregon based on total alkali-silica diagram.

Examples of tubular structures within Antarctic (A-F) and Icelandic (G-L) volcanic glass interpreted as putative
microbial bioalteration textures. Collected using IPM petrographic microscopes.

Backscatter electron images and Li-B element maps of round polished 2.5 cm diameter petrographic thinsections of Icelandic hyaloclastites. Collected using IMS-1280 at IPM.

Backscatter electron image and major element maps of alteration assemblage from the Antarctic Kirkpatrick
Basalt hyaloclastite breccia and Icelandic Laugrvatnsfjall hyaloclastite tuff. Collected using EPMA at IPM.

Spidergrams illustrating the major element compositions of altered glass, and phyllosilicates compared to fresh
unaltered glass. All data plotted was obtained using WDS (EPMA at IPM).

WDS profiles across alteration zones in Antarctic hyaloclastites. Collected using EPMA at IPM.