61st Annual Report on Research 2016

The principal investigator has been involved in data acquisition, data analysis, presentation of research, and overseeing three undergraduate students from Rose-Hulman Institute of Technology during this reporting period. There were additional new experimental research techniques the PI was involved in besides X-ray Absorption Near-Edge Structure Spectroscopy (XANES) method that she usually conducts, as described below. One of the main objectives of the research this year was to gain insights in the micron-level into the various sulfur structures in shales and kerogens that are prone to petroleum generation. The PI conducted a series of experiments at Advanced Light Source in Lawrence Berkeley Laboratory in April 2016. X-ray Absorption (XAS), along with X-ray Fluorescence (XRF) and X-ray Diffraction (XRD) measurements were made on different sections of a shale rock. The samples were first sent to a chemical laboratory to obtain quartz slides thin (30 microns) sections of 1” x 2” samples. These samples are known to contain snail-shaped organic matter called foraminifera. These portions of foraminifera have characteristic large pores, and the organic matter is rich in sulfur. The goal of the experiment was to identify these structures and measure the abundance and speciation of sulfur in these structures. This provides an in-depth look at how the different constituents within a kerogen samples metamorphose to generate petroleum related products. This work resulted in an oral presentation in the annual Petrophase conference this year, and the data analysis involved two undergraduate students. Data Acquisition: During August 2015, the PI and one undergraduate students, Michael Grayson, made a trip to the synchrotron facility Advanced Photon Source (APS) at Argonne National Laboratory (ANL). They collected sulfur K-edge XANES data on different shale, kerogen, and oil derived samples such as petroleum asphaltenes. They were joined there by a research group from Schlumberger-Doll Research (SDR) and two scientists from APS. The data acquisition was very successful. During April 2016, the PI also obtained beamtime as a result of a proposal that she had submitted to Lawrence Berkeley Laboratory Advanced Light Source (ALS). With the three days of beamtime she collected data of XAS, XRD, and XRF all in the micro-range of beam size. This was done at beam line 10.3.2 at the synchrotron radiation facility of ALS. Dr. Sirine Fakra and Dr. Matthew Marcus from ALS collaborated with the PI. The energy of the photons was around the 2372 eV which is at the sulfur K-edge. Three different cross-sections of the sample were studied extensively. Si (111) crystals were used in the double crystal configuration. An Amptek silicon drift fluorescence detector 1-element (XR-100SDD) was used to do the XRF mapping, chemical mapping and record the S K-edge quick Quick X-ray Absorption Near-Edge Spectroscopy (QXANES) spectra. The PI learned about the new micro-techniques which focus on only a small size of the sample (30 microns) of the sample, thus attempting to decipher how the sulfur chemical structures changes from one spot to another. This gives one a better understanding if there are pockets of highly organic matter in the sample as discussed previously. Sulfur QXANES were performed at various spots of the samples. This new method is very useful in the proposed research, and will be used again in more samples from different sources. On-campus work During the summer of 2015 the PI worked on XANES data analysis. Grayson was also employed and he worked on data analysis on the data just collected. This eventually led to a manuscript (see publications at the bottom) where Grayson was one of the co-authors along with two other undergraduate students from RH, and some other scientists. The PI worked on this project and also on a similar project, which resulted in another manuscript eventually(see publications at the bottom) . The PI spent a fair amount of time analyzing the data and preparing manuscripts during this summer. In summer of 2016, the PI, along with two undergraduate students, Dylan Linville and Brandon Keltz were involved in data analysis of all the data that were collected both at APS and ALS. New software programs were written, and newer analysis procedures were tried out. The results have been promising to the extent that Keltz is going to pursue a directed study under the PI during the winter quarter of 2016-17. He will also accompany the PI on a field trip to APS in November, 2016. Presentations The PI presented a 25 minute presentation of the XANES and the XAS, and XRF results recently obtained at the annual Petrophase Conference in Elsinore, Denmark. The presentation was very well received. Two publications: 1. Pomerantz, A.E., Le Doan, T. V., Craddock, P., Bake, K.,Kleinberg, R., Burnham, A., Wu, Q., Zare, R., Brodnik, G., Lo, William C., Grayson, M., Mitra-Kirtley, S., Bolin, T., Wu, T., “Impact of Laboratory-Induced Thermal Maturity on Asphaltene Molecular Structure”, Energy Fuels, 30, 7025?7036, 2016. 2. Bolin, T. B., Birdwell, J. E., Lewan, M. D., Hill, R. J., Grayson, M. B., Mitra-Kirtley, S., Bake, K. D., Craddock, P. R., Abdallah, W., Pomerantz, A. E., "Sulfur species in source rock bitumen before and after hydrous pyrolysis determined by XANES, Energy Fuels, 30 (8), pp 6264–6270, 2016. The next step of the project will be to 1. Collect more data at APS during a beam time in November 2016. 2. Collect more micro-XAS, XRF, and XRD data at ALS during the cycle of late fall 2016. 3. Analyze all the data for new results and trends.