SEM – Energy Dispersive Spectroscopy Pennsylvania Geological Survey BULK MINERALOGY X-ray Diffraction and SEM – Energy Dispersive Spectroscopy Title slide for each presenter’s section –blue/green rectangle border at top; major and minor headings, as per workshop agenda John A. Harper John H. Barnes Kristin M. Carter Pennsylvania Geological Survey

XRD ANALYSIS Title slide for each presenter’s section –blue/green rectangle border at top; major and minor headings, as per workshop agenda

Legacy XRD Data

Distribution of New XRD Data Example slide with map graphics

and Outcrops of Antes Fm. Initial XRD Effort Wells Penetrating Utica/Point Pleasant Fm. and Outcrops of Antes Fm. Well sampled for Reedsville, Utica, and Point Pleasant mineralogy Outcrop sampled for Reedsville, Utica, and Point Pleasant mineralogy

Representative Sample Display

Original XRD Analysis Method Used reference intensity ratio (RIR) method RIR values used by XRD software to perform SEMIQUANTATIVE calculations using statistical analysis. RIR values SHOULD be directly related to the percentages calculated by XRD software White background, dark blue text, and Arial font type to be used for all slides Any single mineral might have several patterns with different RIR values

Results There was no correlation between RIR values and reported percentages “Clay mineralogy is a mess and there is just no way you are going to be able to quantify illite-muscovite phases by RIR.” (contact at equipment vendor) This means that, for other materials associated with the clays, the quantification of those other materials can only be relative.

Updated XRD Analysis Method Equipment vendor suggested switching to Rietveld refinement method Rietveld uses a least squares approach to refine a THEORETICAL line profile until it matches the MEASURED profile Rietveld attempts to recreate the observed diffraction scan via calculation involving structural data for each observed mineral – preferred orientation of minerals with perfect cleavage taken into account Able to deal reliably with strongly overlapping reflections Results: Good analyses with positive results

NEW XRD DATA GENERATED DURING THIS PROJECT API No. State County Location/Well Name Sample Depths (ft) Number of Samples NA PA Various Outcrops in central PA 18 3100705087 NY Broome Richards No. 1 7,400-7,940 25 3102504214 Delaware Campbell No. 1 7,400-8,300 19 3104303993 Herkimer Skranko No. 1 1,550-2,950 26 3110103924 Steuben Olin No. 1 9,500-10,010 20 3110723883 Tioga Beach No. 1 10,000-10,700 35 3404120253 OH Weed No. 1 1,650-1,960 29 3407323283 Hocking Sunday Creek Coal Co. No. 3-S 4,450-4,790 33 3407720028 Huron Newmeyer No. 1 2,568-2,935 32 3408926065 Licking Rowe-Grube Unit No. 1-3613 3,300-3,570 27 3412920089 Pickaway Clutts George & Sue No. 1 1,590-1,960 37 3413920608 Richland Joseph Kruso No. 1 3,210-3,520 3700521201 Armstrong Martin No. 1 11,750-12,020 30 3700920034 Bedford Schellsburg Unit No. 1 7,300-7,700 40 3701990063 Butler Hockenberry No. 1 8,404-8,902 46 3702720001 Centre Long No. 1 13,800-14,250* 2 3703520276 Clinton Commonwealth of PA Tr. 285 No. 1 14,000-14,500 49 3703920007 Crawford Kardosh No. 1 5,870-6,280 44 3704920049 Erie PA Dept. of Forests & Waters Block 2 No. 1 3,705-4,096 3706720001 Juniata Shade Mt. No. 1 3,650-3,900 3708333511 McKean Say No. 1 9,000-9,200 3708520116 Mercer Fleck No. 1 6,650-7,200 57 3708720002 Mifflin Commonwealth of PA Tr. 377 No. 1 5,050-5,350 3710320003 Pike Commonwealth of PA Tr. 163 No. C-1 13,400-13,600 3711120045 Somerset Svetz No. 1 15,000-15,170 16 3711320002 Sullivan Dieffenbach No. 2951 16,050-16,450* 3 3711720181 Marshlands No. 2 11,660-12,130 3712320150 Warren Shaw No. 1 8,047-8,376 48 3712522278 Washington Starvaggi No. 1 10,030-11,010 99 Total Samples 930 NEW XRD DATA GENERATED DURING THIS PROJECT Central PA outcrops Well cutting samples were submitted for XRD analysis from 28 wells in NY, OH, and PA, and from 10 PA outcrops Only a few samples per well 930 samples analyzed

Final Dataset: Wells And Outcrops Sampled For XRD Analysis

Sample XRD Data Table

Representative XRD Data Plot

One Anomalous XRD Data Plot Svetz Well

XRD Data Plot of Svetz Well

Potential use of XRD Data Plots Richards Well HockenberryWell Rowe-Grube Unit Well

UTICA POINT PLEASANT TRENTON LOGANA?

UTICA POINT PLEASANT TRENTON LOGANA?

UPPER INDIAN CASTLE LOWER INDIAN CASTLE TRENTON FLAT CREEK

XRD Plots For Stratigraphic Correlation

Sample XRD Data Presentation for Final Report

SEM – ENERGY DISPERSIVE SPECTROSCOPY Title slide for each presenter’s section – major and minor headings, as per workshop agenda

Distribution of SEM Analyses 74NY5 Since we last met, we also completed our EDS analyses for three PA wells. Last November, I showed you the results for the Hockenberry #1 in Butler County. Today, I’m going to show you results for discrete depth intervals in the Shade Mountain #1 and PA Tract 163 #C-1. Our report, of course, will include all the EDS results for all depths sampled in each well.

EDS Analysis Hockenberry #1 API# 3701990063 Data Number: 002119 Magnification: 1000 Accelerating Voltage: 20000 Volt Emission Current: 68000 nA Working Distance: 15100 um Sub-Signal: BSE2 Vacuum: 10 P Beam: 50 Element Concentration O 56.81 wt% Na 0.93 Mg 1.28 Al 8.44 Si 21.06 S 1.28 K 2.94 Ca 2.87 Ti 0.39 Fe 3.99 S13-013-001 8,504 – 8,513 ft Utica Sh. Butler County, PA Since we last met, we also completed our EDS analyses. I’m going to show results for discrete depth intervals in three PA well locations. First, the Hockenberry #1 from Butler County, PA. This analysis comes from the Utica Shale at a depth of 8504-8513 ft. Inset graph and table: LEFT - Graph of the elements detected. RIGHT - Text file generated to describe the elemental concentrations (weight percent) of the primary elements detected.

Element Maps - Hockenberry #1 You may remember these element maps from my presentation in November 2013. I’m showing this one again for the Hockenberry #1. Upper left – map of calcium (red dots); clusters most likely indicate calcite or dolomite. Lower left – map of magnesium and calcium; there is very little magnesium in this sample, so the carbonate grains are most likely calcite rather than dolomite. Upper right – map of calcium and silicon together AND Lower right – three-color map of aluminum, silicon, and potassium of the same sample; shows an abundance of each element scattered across the map, suggesting that the majority of this sample is a potassium aluminum silicate. Although the distribution of these elements could indicate clay minerals, k-feldspar, and/or other silicate minerals, the XRD analysis associated with this sample found no k-feldspar present. Therefore, the XRD results are consistent with the interpretation that the matrix in this particular Butler County sample is most likely comprised of one or more clay minerals (e.g., illite).

EDS Analysis Shade Mtn. #1 API# 3706720001 3,770 – 3,780 ft Antes Fm. (Point Pleasant Fm. equivalent) Juniata County, PA Data Number: 002127 Magnification: 1000 Accelerating Voltage: 20000 Volt Emission Current: 65000 nA Working Distance: 15000 um Sub-Signal: BSE2 Vacuum: 10 P Beam: 50 Element Concentration O 59.55 wt% Na 0.19 Mg 0.61 Al 4.41 Si 13.98 S 7.93 K 1.54 Ca 8.41 Ti 0.37 Fe 3.00 Here’s the Shade Mountain #1 from Juniata County, PA. This analysis comes from the Point Pleasant Formation at a depth of 3770-3780 ft. Inset graph and table: LEFT - Graph of the elements detected. RIGHT - Text file generated to describe the elemental concentrations (weight percent) of the primary elements detected.

Element Maps - Shade Mtn. #1 Element maps for the Shade Mountain #1 using EDS. Upper left – map of calcium (red dots); notable amount of calcium. Lower left - map of magnesium and calcium; there is very little magnesium in this sample, so the carbonate grains are most likely calcite rather than dolomite. Upper right – map of calcium and silicon together AND Lower right – three-color map of aluminum, silicon, and potassium of the same sample; shows each element scattered across the map, suggesting that the majority of this sample is a potassium aluminum silicate (for example, illite).

EDS Analysis PA Tract 163 #C-1 API# 3710320003 13,440 – 13,450 ft Martinsburg Fm. (Point Pleasant Fm. equivalent) Pike County, PA Data Number: 002129 Magnification: 1000 Accelerating Voltage: 20000 Volt Emission Current: 65000 nA Working Distance: 15000 um Sub-Signal: BSE2 Vacuum: 10 P Beam: 50 Element Concentration O 50.78 wt% Na 0.16 Mg 1.21 Al 1.21 Si 18.93 S 0.63 K 2.19 Ca 6.35 Ti 0.40 Fe 13.31 Also, the PA Tract 163 #C-11 from Pike County, PA. This analysis comes from the Point Pleasant Formation at a depth of 13440-13450 ft. Inset graph and table: LEFT - Graph of the elements detected. RIGHT - Text file generated to describe the elemental concentrations (weight percent) of the primary elements detected.

Element Maps - PA Tract 163 #C-1 Element maps for PA Tract 163 #C-1 using EDS. Upper left – map of calcium (red dots); a fair amount of calcium in this sample as well. Lower left - map of magnesium and calcium; not much magnesium here either, so the carbonate grains are most likely calcite rather than dolomite. Upper right – map of calcium and silicon together – lots of silicon (consistent with Juergen Schieber’s SEM analysis) AND Lower right – three-color map of aluminum, silicon, and potassium of the same sample. These qualitative analyses corroborate the XRD mineralogy results you’ll be seeing in Task 4 of our presentation (John Harper). ON TO MICHELE…