30
A
Class Data:
Dominican Republic Coastal Seawater
25
δ34S (‰) VCDT
δ34S (‰)
20
15
10
1189
5
Relative Depth
0
site locations
Bullion- Fe ADIT-2006
Bullion-S ADIT -2006
B
1188
0.0
2.0
4.0
6.0
δ34S (‰)VCDT
8.0
C
Ranges of S Isotopic Values in Geologic Systems
evaporate sulfate
ocean water
sedimentary rocks
metamorphic rocks
granitic rocks
basaltic rocks
extraterrestrial materials
(meteorites and lunar rocks)
-50
-40
-30
-20
-10
0
10
20
30
40
50
60
δ34S (‰ VCDT)
Range of sulfur isotopes in geologic systems. Note the
difference between mantle-derived S and Sedimentary
sulfides (Hoefs, 1980, fig. 12).
Where do you predict the Henryville
copiapite crust values to fall?
Data
Analysis and
Presentation
Data from
Natural Waters
Ion Values in Griffy Lake and adjoining Fly Ash Retention Ponds
Sampling of several different locations in Griffy Lake as well as sampling of retention
ponds with water occurred in October and November. Seven samples were obtained
from Griffy Lake in October, and eight in November. Six retention pond samples were
taken in October, and eight in November.
Average Cation Values
Lake
Cation Concentrations (meq/L)
Retention Ponds
Ca
6.00
118.73
5.00
4.00
3.00
2.00
1.00
K
Mg
0.00
58.53
Retention
Lake
33.83
4.03 6.53
K (mg/L)
10.45
9.26
12.37
Na
Na (mg/L)
Ca (mg/L)
Mg (mg/L)
Figure 1. – Average cation concentration as observed over several
samplings during October and November from various locations
in Griffy Lake and several retention ponds.
Figure 2. – Calculated cation concentrations from Griffy
Lake and retention pond samplings.
Estimated Anion Values
Lake
Retention Ponds
316.12
178.12
52.19
48.96
17.36
36.48
10.54
NO3 (mg/L)
15.98
Cl (mg/L)
HCO3 (mg/l)
SO4 (mg/L)
Figure 3. – Estimated Anion Values in mg/L as determined by using cation-anion balance with a 5% allowable
error based on observed cation (meq/L) values. The total cation charge was calculated to be 4.31 in the Lake
and 8.69 in the retention ponds, with an acceptable error of +/-0.22 and 0.43 respectively.
Background
Nantucket Island
Fig 1. Location of the study area
7 Dec 2010
Yanyan CHEN
Department of Geological Sciences, IUB
7
Hydrochemical facies
(I) Ca2+ – Mg2+ – Cl- – SO42- Type
(II) Ca2+ – Mg2+ – HCO3-Type
(I)
(III) Na+ – K+– HCO3- Type
(IV)Na+ – K+ – Cl- – SO42- Type
(II)
(IV)
(III)
Fig 2. Piper trilinear diagram showing hydrochemical facies
(HCO3- concentrations are calculated from Ca2+ concentrations)
7 Dec 2010
Yanyan CHEN
Department of Geological Sciences, IUB
8
Water quality assessment
Table 1. The wet chemistry data for test wells (mg/L)
Nitrite
Nitrate Fluoride Chloride Sulfate Phosphate Fe
Mg
Mn
Ca
K
Na
2.16
11.2
0.637
0.855
41.1
0.556
10.4
#193 (08/21/05)
0.09
0.00
22.06
18.7
# 28 (08/20/05)
West end
(08/21/05)
0.26
0.01
21.93
13
2.99
0.10
61.8
13.8
#169 (08/20/05)
1.26
0.16
17.51
38
#302
0.07
0.06
25.40
2.95
0.02
0.00
48.4
34.1
#313 (08/21/05)
0.03
0.05
13.7
27.9
1.11
Long Beach
0.24
0.06
5.04
23.4
3.961 0.915
0.081
3.38
0.920
8.80
5.27
0.193
0.113
0.462
2.92
16.7
#228 (08/20/05)
0.00
1.38
Lloyd
trace
8.86
0.05
8.12
8.6
Smith Point
0.08
0.07
0.01
9.05
4.6
Lido Beach
Atlantic Beach
0.02
0.77
0.06
2.06
12.2
3.57
0.695
0.065
1.72
0.609
6.24
0.12
0.01
703
40.7
1.40
20.4
0.127
42.4
15.9
305.5
10a
4a
250b
250b
0.3b
0.05b
Drinking water
standard
1a
0.02
Drinking water standard is from http://water.epa.gov/action/advisories/drinking/upload/dwstandards2009.pdf
a: Maximum contamination level ; b: Secondary drinking water regulations ; c: From Drinking water Advisory Table
20c
9
Water Well drilled into New Albany
Shale
Samples at depths 1-10
a and b denote
different times
1a
1b
2a
2b
3a
3b
4a
4b
5a
6a
7a
7b
8a
8b
9b
10a
10b
Ca2+ Mg2+ Na+ K+
Cl- NO3- SO42- HCO3
110
30 6.7
47
41 47.3
57 335
76
23 3.3 0.7
16 1.8
93 170
70
23 2.4 0.7
9 80.6
22 159
64
19 4.5 0.5
10 6.4
50 165
59
17 2.7 0.8
5 47.3
22 142
72
23 7.3 0.5
21 0.5
15 167
76
23 4.7 1.5
20 38.3
37 184
66
19
4 0.6
20
5
74 144
55
17 2.9 1.2
23 67.1
22
96
54
16
2 0.7
11
59
18 114
61
18 2.7 0.8
15 82.4
28 100
83
24 4.9 0.6
19 3.6
82 187
68
20 1.8 0.5
15 59.4
19 157
88
26 4.3 0.4
18 8.6
70 220
130
38
28 0.8
41 6.8 130 331
82
26 2.1 0.6
22 6.8
16 193
96
28 3.2 0.6
14 63.5
59 280
• Sulfate drops with depth
• Less sulfate in a than b
• Much more nitrate in a than b
• Something occurred between
times a and b
Ca
a
avg
b
avg
Mg
Na
K
Cl
NO3 SO4
HCO
3
70.55556 21.11111 3.111111 5.977778 17.88889 54.24444 26.77778 164.4444
84.375
25
7.4375
0.5875
19.875
12.025
71.625
208
Fig 2 – Average ion concentrations (mg/L) at time a and b
Fig 1 – Piper diagram of ion
concentrations (%meq/L) in
samples from well in New
Albany Shale at times a and b
Southern Indiana Springs and Seeps
• Sampling occurred on 4 springs and seeps in
Southern Indiana, analyzed for _ and_
• Bedrock geology was predominated by the
Raccoon Creek Group (Pennsylvanian), Buffalo
Willow Group and West Baden Group
(Mississippian)
• Dominate rock types includes shale,
sandstone, and limestone with small amounts
of clay.
Wedge Quarry
Ice Box Spring
Mound Spring
Middle Spring
Figure 1: Diagram shows the general water chemistry of four springs and seeps.
Samples taken in a 1 km2 in French Lick, Indiana in April 2009. Wedge Quarry
seep, Mound Spring and Middle Spring are classified as Ca2+ and HCO3- dominate.
Ice box Spring is Ca2+ and SO42- dominated.
Octopus Spring
•
Yellowstone National Park: Lower
Geyser Basin
•
Discharge of ~80gal/minute
•
Alkaline Hot spring
•
Temp: ~90⁰C pH: ~8.5
•
Temp, pH, SpC, and Eh vary spatially
throughout the right and left forks
•
Supports communities of
Photosynthetic & non- photosynthetic
Bacteria + Algae and Fungi
Octopus Spring. July 2008. Note the blue color of the water
and the orange microbes growing near the siliceous sinter.
•
Blue color in Large Pool is a result of
dissolved silica particles (<10microns).
Water is actually a colloid
Synechococcus
Examining The Data
A:
B:
Figure 1: A; Specific conductivity (mS/cm) and temperature (⁰C) as a function of distance (m) along the right fork of Octopus
Spring, exhibiting a general trend of decreasing SpC with decreasing temperature. B; Specific conductivity (mS/cm) and
temperature (⁰C) as a function of distance (m) along the left fork of Octopus Spring, exhibiting a general trend of decreasing SpC
with decreasing temperature. Octopus Spring. Yellowstone National Park. Erika Elswick and G329. July 4, 2003.
Examining The Data
Figure 2: Eh (mV) and pH as a function of distance along the right fork of Octopus Spring. Eh values range from +100 to
-13 mV. pH values range from 8.5 to 9.0. Octopus Spring. Yellowstone National Park. Sampled by Erika Elswick and
G329. July 4, 2003.
Factors Contributing to Variation:
• Distance from source and water depth affect Temp.
• Rhyolite bedrock contributes dissolved silica
• Temp. affects solubility of silica
• Influence of the microbial community
• Dissolved hydrogen gas
• Lack of hydrogen sulfide contributes to high pH
• Reduced conditions despite exposure to oxygen
Data from
Soils and Sediments
Accumulation of Metals in Western
Pearl Mussel Shells
• Samples collected at Bear Valley Creek, one site was upstream
from dredging, one downstream.
• Data suggests that silica, titanium, strontium, and barium
accumulate in shells downstream from dredging sites.
• Data can be analyzed by looking at average and standard
deviations concentrations of species.
• Analysis could be performed by powdering shells and
digesting them as we did with black shale. These solutions
could be analyzed by AAS or gravimetric analysis.
0.7
90
80
0.6
70
0.5
60
0.4
50
0.3
40
30
0.2
20
0.1
Dredged
10
0
Non
TiO2 (%oxide
SiO2 (%oxide)
X 100)
Dredged
0
Dredged
Not
Dredged
It appears that peak TiO2, SiO2,
Ba, and Sr levels correspond to
the same samples. This may be
due to dredging that grinds
metal-rich igneous bedrock and
inputs cation species into the
water. These minerals may be
precipitated with Ca when the
bivalves create their shells, and
are locked into the shells
permanently. The minerals
released in dredging occur
when mining Fe, Mn, Nb, and
Ta ores, which are due to
contact metamorphism of
granites.
Carmichael Creek
P 2 O5
0.4
0.35
0.3
wt. %
0.25
O
0.2
A
0.15
B
0.1
0.05
0
4S
3S
2S
1S
1N
2N
3N
4N
Figure 1. This graph shows the weight % of P2O5 determined from soil
samples taken along a vegetation transect. The transects were located on
north and south facing slopes within Carmichael Creek valley in Montana.
The x axis labels tell the position of the transect relative to the creek (1S
representing the samples closest to the stream on the south facing slope).
The blue represents the O-horizon, the red represents the A-horizon and
the green represent the-B horizon. The detection limits were to 0.02 wt%.
MgO
K2O
5
3
4.5
2.5
4
3.5
wt. %
O
2.5
A
2
B
1.5
wt. %
2
3
O
1.5
A
B
1
1
0.5
0.5
0
4S
3S
2S
1S
1N
2N
3N
4N
Figure 2. This graph shows the weight % of
MgO from soils samples taken within
Carmichael Creek Valley in Montana. The soils
were taken along a vegetation transect on
north and south facing slopes, represented
with an N or S on the x-axis with the numbers
moving from 1 to 4 relative to distance from
Carmichael Creek. The blue represents the Ohorizon, the red represents the A-horizon, and
the green represents the B-horizon.
0
4S
3S
2S
1S
1N
2N
3N
4N
Figure 3. This graphs shows the wt.% of K2O
of soil samples taken along a vegetation
transect in Montana. The x-axis labels
represent distance from Carmichael Creek
and location on either on the north or south
facing slope, 1 being closest to the creek.
The blue represents the O-horizon, the red
represents the A-horizon, and the green
represents the B-horizon.
Montana Soils
Nickel concentration by
elevation
60
y = -0.129x + 738.96
R² = 0.617
40
30
20
10
0
5350
5400
5450
5500
Elevation (ft)
5550
5600
5650
Mo Concentration (ppm)
2.5
50
Ni Concentration (ppm)
Molybdenum concentration by
elevation
2
1.5
1
y = 0.0051x - 26.672
R² = 0.8593
0.5
0
5350
5400
5450
5500
5550
5600
Elevation (ft)
Figure 1. Nickel and molybdenum concentrations are plotted against
elevation. Data is from soil samples taken in 2003 as a belt transect up a
valley wall near the South Boulder River in southwestern Montana. High
nickel concentrations at the lower elevations indicate a possible intrusion.
As elevation increases, other elements such as molybdenum have a higher
relative concentration, indicating lack of influence from an intrusion.
5650
Montana Soils
y = 0.0301x - 1.4334
R² = 0.7581
Total Organic Carbon vs Zinc
9
8
7
TOC (%)
6
5
4
3
2
1
0
125
145
165
185
205
225
245
265
285
305
Zn Concentration (ppm)
Figure 2. Total organic carbon is plotted against zinc concentration. Data is from
soil samples taken in 2003 as a belt transect up a valley wall near the South
Boulder River in southwestern Montana. The graph indicates moderate correlation
with an R2 value of 0.758.
Soils from abandoned agricultural
fields near Bloomington, IN
600
Garvey 41.8
500
Garvey 65.6
400
Garvey 69.6
300
Garvey 85
Garvey 114.4
200
Griffy 9
100
Griffy 42
0
Griffy 64
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
(ppm)
Mo
Sn
Zr
Sr
Rb
U
Th
Pb
Zn
Cu
Ni
Co
Cr
V
Ba
Griffy 71
Concentrations of trace elements in ppm. Depth increases from darker to lighter colors
•GRI-Sanders Group Limestone
•GAR-West Baden Group (shale, mudstone, sandstone, some limestone)
•Ni, Co, Cr, V, and Zn appear to be mobile in Garvey soil accumulating near
the bottom of the profile possibly due to a clay rich B-horizon and a higher
water table.
•Zr appears to be mobile, but the other elements appear to be accumulating
near the top of the profile. The plant cover is much different at the Griffy site
which may account for accumulation in the A-horizon due to more biological
activity.
Aegina Clays - Greece
• Four suggested clay groups: marls, epiclastic flows, alluvial clays
and terra rossa soils.
• Epiclastic flow clays are characterized with the highest content of
SiO2 (50.91 – 62.66%) and Al2O3 (12.71-19.32%).
• The marl clays are characterized with the low silica content and the
highest content of both CaO (16.11-51.86%) and total C (3.2311.96%). Also, they show the highest values of LOI.
• The terra rossa soil clays have concentrations of SiO2 and Al2O3
that are close to the concentrations of epiclastic flow clays, BUT
they have higher Fe2O3 and K2O content.
• Alluvial clays don’t show a characteristic signature, but can be
compared to the previous groups by having SiO2 and Al2O3 contents
higher than that of marl clays and lower than that of the epiclastic
flow clays. CaO and total carbon are intermediate between the two
groups too.
• Is sample A82 epiclastic flow or alluvial clay? Comparing the
concentrations of Al2O3, CaO, total C, NaO and Ba in this sample,
it belongs to the group of epiclastic flow.
Different clay samples from Aegina – Greece. The diagrams show that samples of each group
have very close behavior and cluster together. Two marl sample are away from the other marl
samples because of their low SiO2 content, they might be limestones. Sample A82 is closer in
its chemical behavior to the epiclastic flow clays as figures A and B show.
Lerna, Greece Sediments
• Lerna was known throughout
•
•
Ancient Greece for its pure spring
water.
Modern-Day Lerna is just south of
the city of Argos, an ancient citystate known for its harbor.
Hercules slayed the Hydra at Lerna.
• The underlying geology is a Karst
system with mountains to the West.
• 10 sites around Lerna were sampled
and the sediments (<10,000 years
old) were analyzed for major
oxides, trace elements, LOI, and
total carbon/sulfur.
 I theorized that these coastal plain sediments
were weathered from:
• Low-Si igneous rocks from the western
mountain range, based on average Si content
• Underlying carbonate system, due to the high
CaO levels relative to other oxides and the high
TOT/C.
 All of the samples appear to be from the same
parent materials. Both major oxides and trace
elements align closely, with no major outliers.
 Very high concentration of Ni, which is
commonly mined in Greece.
Organic component of coastal plain sediments from Lerna,
Greece, by Hannah Timm from Christina Shriner’s collection.
Samples
GSC
UG
UPa
LUG
LMG
LLG
MZ
LS
U of P
L of P
LOI
%
16.4
21
19.7
17.8
17.9
18.4
19.6
17.1
15.7
14.7
TOT/C
%
2.68
4.9
3.95
2.76
3.03
3.39
4.14
3.69
2.43
2.19
TOT/S
%
0.02
0.01
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.01
250
60
GSC
50
UG
200
UPa
40
LUG
150
LMG
wt. %
ppm
30
LLG
20
MZ
100
LS
10
U of P
50
L of P
0
0
Mo Cu Pb Zn
Ni
Major oxides in wt. % and trace elements in ppm analyzed from coastal
plain sediments from Lerna, Greece, by Hannah Timm from Christina
Shriner’s collection. No date.
As Cd Sb
Bi
Ag Au Hg Ti
Se
Data from
Sedimentary,
Metamorphic and Igneous
Rocks
Rio Maton Mid-Cretaceous
sediments, Puerto Rico
Mixture of carbonates, volcanoclastics and mudstones
Geochemistry shows a general increase in TS and
decrease in TIC up section (deepening upward cycle)
More of a shallow marine environment in the lower
portion with transitional to deep marine as you move
upward in section
Cretaceous
• This was a greenhouse time dominated by sea-floor
spreading and elevated CO2 levels
• The lower portion shows higher TIC than the upper
portion which indicates more shallow-marine to
lagoonal environment (brackish- normal marine)
• As you go vertically through the section you will find a
general decrease in TIC. This can be interpreted as a
deepening upward cycle where accommodation is
higher than the shallower, lower section leading to an
increase in siliciclastic dilution
Data Set
TS (wt%)
TIC (wt%)
0.0800
35.000
0.0700
30.000
0.0600
15.000
10.000
Wt% TIC
20.000
5.000
0.000
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Fig 1: This data set shows sample numbers on the
x-axis which is assuming that 1 is the top of the
section and 25 is the bottom of the section. It is
clear that there are at least 3 deepening upwards
cycles where the bottom half of the section is
dominated by limestone (sample 13-25) and from
sample 13 on begin the cycle of deep marine and
more of a siliciclastic input.
Wt% TS
25.000
0.0500
0.0400
0.0300
0.0200
0.0100
0.0000
1 2 3 4 5 6 7 8 9 10111213141516171819202122232425
Fig 2: Assuming that 1 is the top of the section,
the data shows the bottom portion to have lower
TS values than the upper portion. This is due to an
overall deepening trend with more accommodation
for silicilcastics. Where as the bottom part of the
section was more of shallow marine/lagoonal
environment.
•Devonian-Mississippian Black Shale, Northern
Kentucky
•These elements seemed the most influential in
determining the lithologic boundaries.
•As you can see, these elements show fairly
constant trends throughout the core.
•Marine vs. Non-Marine input
- these elements are often associated with
marine environments
- seesaw affect due to river setting
•There was almost no Uranium but some thorium
- Uranium binds with Oxygen leaving Thorium
behind
- Thorium has been put to use as a Nuclear
Energy Source
•Explanation for Zinc?
Core Depth vs. Ion Concentration
5000
4500
4000
Concentration (ppm)
3500
3000
2500
Zr
Pb
2000
Zn
1500
Co
1000
500
0
0
5
10
15
20
25
30
35
Core Depth (m)
Figure 1.
The above figure analyzes the different concentrations (ppm) of Zr, Pb, Zn, and
Co for the Devonian-Mississippian Black Shale in Northern Kentucky
collected in 2000, plotted against core depth (m). The different colored lines
are denoted on the figure’s legend above.
Devonian-Mississippian Black Shale,
Northern Kentucky
• The graph on the previous slide shows that
the elements are not very mobile and resist
weathering
• Through research I found that this area is
marked as a Pb-Zn deposit region according to
the USGS
• This data suggests alluvial deposits which are
typical in river regions due to river currents
• Igneous?
•Organic-rich, black shale deposited in the Illinois Basin
•Late Devonian to Mississippian in age
•Six major members:
•Ellsworth
•Clegg Creek
•Camp Run
•Morgan Trail
•Salmier
•Blocher
•Major source of hydrocarbons
Figure 1. Geographic location of
the New Albany Shale and
Illinois Basin
Three big questions…
 These black shales are organic rich, which
elements correlate well with organic matter?
 Are there any geochemical reasons for the
lithologic determinations for the Shale member
designations?
 How would you geochemically determine if these
were marine or brackish sediments?
Which elements are related to organics?
Zn (ppm) vs. TOC (%)
250
Ni (ppm) vs. TOC (%)
350
200
250
Ni (ppm)
Zn (ppm)
300
200
150
100
150
100
50
50
0
0.00
5.00
10.00
TOC (%)
15.00
0
0.00
5.00
10.00
TOC (%)
15.00
Cu (ppm) vs. TOC (%)
350
300
Cu (ppm)
Figure 2. Zn, Ni, and Cu plotted against
total organic carbon. The positive,
roughly linear trend illustrates the
dependence these metals have on
organic compounds.
250
200
150
100
50
0
0.00
5.00
10.00
TOC (%)
15.00
Geochemical reasons for member
separations?
Nb/Y
20.0
18.0
16.0
Figure 3. Relationship of Zr/Y and Nb/Y for Salmier
and Blocher Members of the New Albany Shale. The
Salmier member is much more clustered in both
cases, with the Blocher member being slightly lower
in Zr and Nb, as well as less clustered.
Nb (ppm)
14.0
12.0
10.0
Salmier
8.0
Blocher
6.0
4.0
2.0
0.0
0
10
20
Y (ppm)
30
40
Zr/Y
250
200
Zr (ppm)
 Selmier Member
 Average TOC 2.06%
 Higher TiO2 (avg 0.91%)
 Higher Zr, Nb?
 Blocher member
 Average TOC 7.21%
 Lower TiO2 (avg 0.64 %)
 Lower Zr, Nb?
150
Salmier
100
Blocher
50
0
0
10
20
Y (ppm)
30
40
Geochemical determination of
brackish or marine sediments
 Brackish water is generally more oxic—these
sediments are euxinic
 Re and Mo concentrations after Crusius et al 1996
 Less diagenetic pyrite in sediments from brackish
waters
 High organic carbon to pyrite sulfur ratio (Berner et al.
1984)
Niobrara Chalk and Shale from Nebraska
The shale and chalk in the Niobrara were deposited in
the Late Cretaceous.1
Shale (Oil/Black) :
The Niobrara Shale is thick, rich in organics and
thermally mature.2
South Dakota
Idaho
Chalk:
Extensive chalk deposition during the Late Cretaceous.
High porosity and low permeability. Gas production
(organic chalk beds). 1
Utah
Data:
The core samples were collected from Nebraska.
This was collected on 1999 and the data that was
provided was done by X-ray Fluorescence.
Table 1: % Oxides: Fe, Mn, Ti, Si, Al, Ca, K, P, Mg, Na with
LOI and total oxides.
Table 2: Trace elements: Mo, Nb, Zr, Y, Sr, U, Rb, Th, Pb,
Zn, Cu, Ni, Co, Cr, V, Ti, Ba. Detection limits of each
element.
17 samples ( 8 High Ca (Chalk) and 9 Low Ca (Shale) ).
Wyoming
Nebraska
Colorado
Kansas
Fig 1: Map showing the Niobrara Shale (red outline).
Source: Unconventional Gas Center web site.
www.ugcenter.com/Shales/US/Niobrara/
1: Watney 2010
2: Unconventional Gas center. 2010
700
High Ca Samples
High Ca samples
600
Zr
400
%
Quantity (ppm)
500
Sr
Rb
300
50.0
40.0
30.0
20.0
10.0
0.0
Cu
200
Cr
Sample I.D.
100
LOI
0
B-7-24
B-7-26
B-7-30
CH-1
CH-9
WB-1
WB-2
WB-3
Sample I.D.
Fig4: Quantities of trace elements Zr, Sr, Rb, Cu, and Cr were plotted for the high Ca samples. The
samples are from cores that were taken from Nebraska (Niobrara chalk and shale, 1999). These
elements were chosen for noticeable differences from low Ca samples.
The trace elements were extracted by XRF.
700
Fig2: The Loss on ignition percentage of all
oxides in the high Ca samples of the
Niobrara chalk and shale core from
Nebraska on the year 1999 and done by
XRF were plotted with each sample .
Low Ca samples
Low Ca samples
600
%
Quantity (ppm)
500
Zr
400
Sr
300
Rb
200
Cu
50.0
40.0
30.0
20.0
10.0
0.0
Sample I.D.
Cr
100
LOI
0
BG-8
B-7-8
M-5-38 M-5-22 B-7-15
BG-2
M-7-9
RBAB3
PR-1
Sample I.D.
Fig5: Quantities of trace elements Zr, Sr, Rb, Cu, and Cr were plotted for the low Ca samples. The samples
are from cores that were taken from Nebraska (Niobrara chalk and shale, 1999). These elements were
chosen for noticeable differences from high Ca samples. The trace elements were extracted by XRF.
Fig3: The Loss on ignition percentage of all
oxides in the low Ca samples of the
Niobrara chalk and shale core from
Nebraska on the year 1999 and done by
XRF were plotted with each sample .
Eocene Siltstones of the Eastern Mediterranean
• House tiles from ancient Mediterranean long-houses.
• These are whole slabs of stone (imagine slate roof-tiles from houses in the
Midwest) not baked clay tiles.
• Question: What is the origin of these house tiles?
• Have samples from various rock outcroppings house builders could have used:
• K1, SQ, PH, PF, TF, PFH, CS1, CS2, GS & XRS
• Have samples of tiles from two different houses:
• AS#74
• HTSC-2 to HTSC-20
• Tile and Bedrock were analyzed for minerals (SiO2, Al2O3, Fe203, etc.) and rare
elements (Ba, Co, Nb, Rb, etc.) as well as organic matter and sulfur.
• I used plots of mineral and rare elements to determine :
• Are all HTSC tiles are related? (Q1)
• Are AS and HTSC tiles are related? (Q2)
• What bedrock types may be related to each type of tile? (Q3)
8.00
TF
GS
7.00
PFH
CS2
PH
6.00
PF
5.00
4.00
CS1
2.00
XRS
PF
1.00
1.00
a
10.00
b
AS
HTSC
1400.0
1200.0
GS
1000.0
800.0
600.0
CS2PH
400.0
TF
CS1
K1
SQ
PFH
XRS
200.0
PF
0.0
0.0
200.0
400.0
Sr
600.0
PH
PFH
XRS K1
0.00
100.00
Ca0 %
Bedrock
Ba
CS2TF
CS1
SQ
3.00
SQK1
0.10
c
GS
K2 O %
MgO %
5.00
4.50
4.00
3.50
3.00
2.50
2.00
1.50
1.00
0.50
0.00
0.10
1.00
Na2O %
10.00
Figure 1. Bivariat plots of concentrations (weight
percent) of major oxides of (a) MgO and CaO (b) Na2O
and K2O and trace elements (c) Ba and S in samples of
Eocene siltstones (blue diamonds) and two types of
stone house tiles HTSC (green triangles) and AS (red
square) from the eastern Mediterranean. Red circles
indicate siltstone samples similar to AS tile samples and
green circles indicate siltstone samples similar to HTSC
samples. Labels on siltstone indicate siltstone collection
site. Subsamples of each stone and tile were analyzed via
INAA for trace elements and major oxides. Erika Elswick
et al. 2010.
Eocene Siltstones of the Eastern Mediterranean
Q1: Are all HTSC tiles are related? (Q1)
Yes, HTSC samples are related to one another. They probably came from
the same source material. (Fig. 1)
Q2: Are AS and HTSC tiles are related? (Q2)
No, the AS#74 sample is not related to the HTSC sample. It may have been
quarried from a different location. (Fig. 1)
Q3: What bedrock types may be related to each type of tile? (Q3)
AS samples seem chemically related to PH and CS samples while HTSC
samples appear to be related to PF and PFH samples. Some samples like
XRS, K1 and GS don’t appear to be related to any of the tiles. (Fig. 1)
Metamorphic Rocks from the Connecticut
River Valley
Samples Fe2O3 MnO
TiO2
SiO2
Al2O3
CaO
K2O
wt%
wt%
wt%
wt%
wt%
wt%
wt%
P2O5
MgO
Na2O
LOI
wt%
wt%
wt%
wt%
Total
FeO
wt%
wt%
JB-001
10.02
0.134
1.63
46.53
18.74
9.56
2
0.952
5.73
2.97
0.92
99.18
9.11
JB-002
9.56
0.128
1.56
46.7
18.75
9.55
2.06
0.942
5.86
3.21
0.84
99.14
8.69
JB-003
9.96
0.135
1.67
46.14
18.68
9.7
1.93
0.964
5.94
3.21
0.83
99.16
9.06
JB-004
9.91
0.1
2.29
48.09
19.52
8.21
2.61
0.816
4.57
2.86
0.76
99.75
9.01
JB-008
7.94
0.134
0.48
48.52
15.81
14.12
0.35
0.051
10.8
1.41
0.78
100.4
7.21
JB-011
7.33
0.113
0.29
47.65
16.3
14.45
0.4
0.029
11.58
1.08
1.11 100.33
6.66
JB-012
6.98
0.101
0.35
46.79
18.64
14.68
0.56
0.017
10.46
0.91
1.13 100.62
6.35
JB-016
5.97
0.082
0.36
47.62
20.48
14.87
0.4
0.034
8.7
1.22
0.6 100.34
5.43
JB-017
6.5
0.09
0.53
47.34
17.24
14.84
0.5
0.046
11
1.19
1.13 100.41
5.9
JB-022
9.39
0.123
1.61
47.24
22.09
13.03
0.19
0.017
5.22
1.67
0.65 101.23
8.54
JB-027
9.1
0.124
1.68
48.31
18.86
8.65
2.57
0.815
4.72
2.86
2.03
99.71
8.27
JB-030
9.15
0.124
1.8
47.59
19.58
9.01
2.21
0.894
5.38
3.1
0.65
99.49
8.32
JB-034
9
0.116
1.32
49.57
19.21
8.94
2.3
0.72
4.17
3.43
0.87
99.64
8.18
JB-038
11.45
0.16
1.13
46.83
18.61
12.52
0.19
0.161
7.17
2.02
0.6 100.84
10.41
JB-039
5.98
0.049
0.64
49.38
25.56
12.84
1.2
0.077
3.03
1.41
0.67 100.84
JB-040
11.15
0.164
2.08
41.62
18.51
11.32
1.89
1.179
7.3
2.69
1
98.91
10.14
JB-042
9.78
0.173
1.56
46.85
18.59
9.7
1.86
0.946
6.44
2.92
0.59
99.41
8.89
JB-043
7.04
0.05
0.67
45.64
27.12
14.22
0.81
0.218
2.4
1.52
0.78 100.47
JB-044
7.38
0.058
0.8
45.02
27
14.32
1.01
0.287
2.58
1.44
JB-046
9.36
0.15
0.26
47.53
10.11
11.7
0.45
0.034
17.3
JB-047
8.23
0.06
1.2
46.38
24.97
12.04
1.78
0.309
JB-052
9.7
0.127
1.58
46.25
19.05
9.84
2
0.939
JB-053
7.63
0.125
0.42
47.64
12.42
14.35
0.48
JB-058
9.16
0.113
1.56
48.18
19.72
8.89
JB-060
8.79
0.122
1.69
48.95
19.64
8.55
http://pubs.usgs.gov/of/2003/of03-225/of03-225.pdf
0.5
5.44
6.4
100.4
6.71
1.58
2.07 100.54
8.51
3.15
1.59
1.08 100.79
7.48
5.82
2.66
1.18
99.14
8.82
0.046
14.37
1.35
1.27
100.1
6.94
2.52
0.849
4.4
3.29
0.86
99.54
8.33
2.67
0.84
4.2
3.21
0.97
99.62
7.99
A
B
Figures A-D: XRF data of Connecticut River
Valley plotted on Ternary diagrams. Plot A: ACF,
B: AFM, C: AKF, and D: CSiFM. Data was
normalized in order to plot on ternary
diagrams. Plot A shows potential for two
metamorphic suites harder to distinguish more
than one suite with other plots.
C
D
Q1:Are there any trends that indicate there are one or more groups of samples?
Q2:What set of elements is the most diagnostic in making your determination?
A1: Definitely one, maybe two at the most.
A2: Aluminum and Iron most helpful
Geochemistry of Extrusive Igneous Rocks
• Mystery basalts collected in 1999: Trace elements
by XRF
• Important elements analyzed: major oxides (Si,
Ti, Al, Fe, Mn, Mg, Ca, Na, K, P); trace elements LILE (Li, Be, Rb, Cs, Sr, Ba); HFSE (Zr, Nb, Ta, Hf, U,
Th)
• Common minerals: silicates – Ti in Rutile, Fe in
Illmenite, Mn in Olivine, other majors and LILE in
Plag, Zr in Zircons, Cr in Spinels; metals in
disseminated sulfides (Po, Pn, Ccp, Py, Sph, Gal)
or oxides (Mag, Hem)
• Discrimination plots with trace elements:
– immobile vs. mobile (enriched by concentration), i.e.
Zr vs. Ti
– Spidergrams with mantle normalized metals
Geochemistry of Extrusive Igneous Rocks
Group A
Group B
Figure 1: Tectonic discrimination plots for the Bikou Group basalts and Mystery basalts. Ti versus
V plot of Shervais (1982). The fields of arc tholeiite, calc-alkaline basalts, mid-ocean-ridge basalt
(MORB), continental flood basalts, and ocean-island and alkali basalts were drawn by Rollinson
(1993) according to Shervais (1982). From: Wang, X. et al. Geological Society of America Bulletin
2008;120:1478-1492
Geochemistry of Extrusive Igneous Rocks
Group A
Group B
Figure 2: Tectonic discrimination plots for the Bikou Group basalts and Mystery basalts. Ti versus
Zr plot of Pearce and Cann (1973). From: Wang, X. et al. Geological Society of America
Bulletin 2008;120:1478-1492
Geochemistry of Extrusive Igneous Rocks
Interpretations:
• An order of magnitude enrichment in concentration of Zr and LILE
suggests Group A is more fractionated than Group B (Table 1)
• Calc-alkaline MORBs of Group B, and possibly arc tholeiites of Group
A (Fig. 1)
• Calc-alkaline magmatic affinity of all Mystery basalts, note more
fractionated Group A again (Fig. 2)
• Both groups fractionated with respect to mantle:
– depletion in Mo and Pb could be attributed to their mobility
– depletion in Ni, Co and Cr and enrichment in Ti could be
attributed to fractional crystallization (depletion via removal of
minerals that contain these elements, and the enrichment by
concentration) (Fig. 3).