1. 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

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

3. Legacy XRD Data

4. Distribution of New XRD Data
Example slide with map graphics

5. 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

6. Representative Sample Display

7. 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

8. 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.

9. 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

10. 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 NY
Broome
Richards No. 1
7,400-7,940 25
Delaware
Campbell No. 1
7,400-8,300 19
Herkimer
Skranko No. 1
1,550-2,950 26
Steuben
Olin No. 1
9,500-10,010 20
Tioga
Beach No. 1
10,000-10,700 35 OH
Weed No. 1
1,650-1,960 29
Hocking
Sunday Creek Coal Co. No. 3-S
4,450-4,790 33
Huron
Newmeyer No. 1
2,568-2,935 32
Licking
Rowe-Grube Unit No
3,300-3,570 27
Pickaway
Clutts George & Sue No. 1
1,590-1,960 37
Richland
Joseph Kruso No. 1
3,210-3,520
Armstrong
Martin No. 1
11,750-12,020 30
Bedford
Schellsburg Unit No. 1
7,300-7,700 40
Butler
Hockenberry No. 1
8,404-8,902 46
Centre
Long No. 1
13,800-14,250* 2
Clinton
Commonwealth of PA Tr. 285 No. 1
14,000-14,500 49
Crawford
Kardosh No. 1
5,870-6,280 44
Erie
PA Dept. of Forests & Waters Block 2 No. 1
3,705-4,096
Juniata
Shade Mt. No. 1
3,650-3,900
McKean
Say No. 1
9,000-9,200
Mercer
Fleck No. 1
6,650-7,200 57
Mifflin
Commonwealth of PA Tr. 377 No. 1
5,050-5,350
Pike
Commonwealth of PA Tr. 163 No. C-1
13,400-13,600
Somerset
Svetz No. 1
15,000-15,170 16
Sullivan
Dieffenbach No. 2951
16,050-16,450* 3
Marshlands No. 2
11,660-12,130
Warren
Shaw No. 1
8,047-8,376 48
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

11. Final Dataset: Wells And Outcrops Sampled For XRD Analysis

12. Sample XRD Data Table

13. Representative XRD Data Plot

14. One Anomalous XRD Data Plot
Svetz Well

15. XRD Data Plot of Svetz Well

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

17. UTICA POINT PLEASANT TRENTON
LOGANA?

18. UTICA POINT PLEASANT TRENTON
LOGANA?

19. UPPER INDIAN
CASTLE
LOWER INDIAN
CASTLE
TRENTON
FLAT CREEK

20. XRD Plots For Stratigraphic Correlation

21. Sample XRD Data Presentation for Final Report

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

23. 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.

24. EDS Analysis Hockenberry #1 API# 3701990063
Data Number:
Magnification: 1000
Accelerating Voltage: Volt
Emission Current: nA
Working Distance: um
Sub-Signal: BSE2
Vacuum: 10 P
Beam: 50
Element Concentration
O 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 S
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 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.

25. Element Maps - Hockenberry #1
You may remember these element maps from my presentation in November 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).

26. EDS Analysis Shade Mtn. #1 API# 3706720001
3,770 – 3,780 ft
Antes Fm.
(Point Pleasant Fm.
equivalent)
Juniata County, PA
Data Number:
Magnification: 1000
Accelerating Voltage: Volt
Emission Current: nA
Working Distance: um
Sub-Signal: BSE2
Vacuum: 10 P
Beam: 50
Element Concentration
O 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 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.

27. 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).

28. 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:
Magnification: 1000
Accelerating Voltage: Volt
Emission Current: nA
Working Distance: um
Sub-Signal: BSE2
Vacuum: 10 P
Beam: 50
Element Concentration
O 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
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.

29. 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…