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Applications of Rare Earth Elements in Geological Studies: A Seminar Presentation BY
Applications of Rare Earth Elements in Geological Studies: A Seminar Presentation BY
GEOLOGICAL STUDIES
A SEMINAR PRESENTATION
BY
JANUARY, 2016
OUTLINE
• Introduction
• Objectives of Seminar
• Classification of Rare Earth Elements
• Geology and Abundance of Rare Earth Elements
• Application OF REEs in Geological Studies
• Case Studies
INTRODUCTION
Table 2. Periodic table of the elements showing the division between LREEs and HREEs (Schuler et al., 2011).
CLASSIFICATION OF RARE EARTH ELEMENTS
Table 3 Rare Earth elements—overview of selected characteristics (Zepf, 2013)
GEOLOGY OF RARE EARTH ELEMENTS
Scandium Sc 21 16.0 na
Yttrium Y 39 22 na
Lanthanum La 57 30 0.34
Cerium Ce 58 64 0.91
Neodymium Nd 60 26 0.64
Promethium Pm 61 na na
Figure 2. Geologic map of the Main and East iron-REE-niobium ore bodies at Bayan Obo,
China (Chao et al. 1997).
GEOLOGY OF RARE EARTH ELEMENTS
Table 6. Minerals that contain REEs and occur in economic or potentially economic deposits (Mariano,1989a)
GEOLOGICAL APPLICATION OF REEs
5. Geochronology
• REE isotopes, particularly of neodymium and
samarium, have found use in petrogenetic modelling
and geochronology
6. Nd isotopes serve as a pointer to changes in erosional
input, sedimentation rates and ocean circulation in
marine sediments (Dahlqvist et al., 2005)
7. Neodymium isotopes in planktonic foraminifera
records the response of continental weathering and
ocean circulation rates to climatic change (Vance and
Burton, 1999).
Case study One
Introduction
The Oshosun Formation in eastern Dahomey Basin, southwestern Nigeria consists
of shale sediments, which are significant for their phosphorite and pyrite
compositions and are fossiliferous. The shales are lower Eocene-middle Eocene
age, are well laminated and contain glauconitic grains.
The study area for this work is located at Sagamu quarry of the West African
Portland Cement (WAPCO) where the sedimentary section is exposed.
The result of this study was used to predict the shale sediment precursors and
Source rock type to enhance the geological knowledge of the shale build-up.
Case study One (cont.)
Methodology
Five (5) selected shale samples were analysed for their rare earth elements by
Neutron Instrumental Activation Technique. This method involves the irradiation
of samples together with a standard with neutron flux. REEs content in the
samples were determined by comparing their residual counts after cooling from a
reference standard irradiated under the same condition as samples. The standard
used in this study is DMMAS-16-1.
The results show a slight enrichment in the light rare earth elements but a
significant depletion in the heavy REE similar to the seawater derived shales. This
signifies that the shale precursors are granitic rocks with large proportions of alkali
feldspars and low contents of plagioclase feldspars.
The enrichment of Ce indicates that the Oshosun shales have undergone some
degree of phosphatization leading to the precipitation of phosphate minerals.
Case Study Two
Introduction
The study areas, Lower Benue Trough is divided into Asu River Group (ARG) and
Cross River Group (CRG) and it is delimited by longitudes 7°00'E and 8°30'E and
latitudes 5°00'N and 6°30'N. ARG covers Awi, Abakaliki and Mfamosing Formations
while Ekenkpon, Eze-Aku, New Netim, Awgu and Agbani Formations fall within
CRG.
The study aimed at using geochemical approach through rare earth elements
(REE) to deduce provenance and depositional environment.
Case Study Two (cont.)
Figure 1. Correlation chart of all outcrops studied showing their locations, formations and groups.
Case Study Two (cont.)
Methodology
A total of 56 fresh outcrop samples collected from eight (8) Formations: Awi,
Abakaliki, Mfamosing Formations which constitute ARG and Ekenkpon, Eze-Aku,
New Netim Marl, Awgu, Agbani Formations which constitute CRG were obtained
from the study area.
The samples were subjected to detailed lithologic description by visual
examination. Geochemical analysis was done using Inductively Coupled Plasma
Mass Spectroscopy (ICP-MS) to determine trace and rare-earth elements using
lithium metaborate/tetraborate fusion method.
Introduction
• In this study, REE geochemical investigations were targeted on oils generated
in the Woodford shale and overlaying Mississippian formation located in the
Anadarko Basin, north-central Oklahoma.
• The REE distribution patterns and total concentrations of the organic matter of
the Woodford shale reveal a potential avenue to investigate hydrocarbon
maturation processes in a source rock.
• This study provides a valuable insight into the understandings of the REE
landscapes in the organic fraction of the Woodford Shale in northern Oklahoma,
linking these understandings to the REE analysis of an oil generated from the same
source bed and comparing it to oil produced from younger Mississippian oil. The
information gathered from this study may ultimately prove useful to trace the
chemical history of oils generated from the Woodford Shale source beds.
Regional Paleozoic Stratigraphic column in the Anadarko Basin.
Case study Three (cont.)
Methodology
• Ten samples of the organic matter fraction and 10 samples of the silicate-
carbonate fraction of the Woodford shale from north central Oklahoma were
analyzed by methods developed at Kansas State University. Thirteen oil samples
from Woodford Devonian oil and Mississippian oil samples were analyzed for REE
by inductively coupled plasma mass spectrometry (ICP-MS) and inductively
coupled plasma atomic emission mass spectrometry (ICP-AES). .
Results and Interpretation
• REE concentration levels in an average shale range from 170 ppm to 185 ppm, and
concentration levels in modern day plants occur in the ppb levels.
• The REE concentrations in the organic matter of the Woodford Shale samples
analyzed ranged from 300 to 800 ppm. The high concentrations of the REEs in the
Woodford Shale, as compared to the modern-day plants, are reflections of the
transformations of buried Woodford Shale organic materials in post-depositional
environmental conditions with potential contributions of exchanges of REE coming
from associated sediments.
Case study Three (cont.)
• The REE distribution patterns for the Mississippian oil samples show a general
LREE enrichment with a minor MREE enrichment. Five out of the seven samples
have a Cerium negative anomaly and all of the samples have a Europium positive
anomaly.
• The Devonian oil samples have REE distribution patterns with a general LREE
enrichement, and a more prominent MREE enrichment is noticeable, when
comparing this samples to the Mississippian oil samples. Three out of the six
samples have cerium depletion and like the Mississippian oil samples, they show
europium enrichment.
Case Study Four
Evaluating rare earth elements as a proxy for oil-source correlation. A case study
from Aer Sag, Erlian Basin, northern China
P. Gao et al., 2015
Introduction
• Traditional geochemical tools for oil-source correlation such as biomarkers and
carbon isotopes can be hampered by thermal maturation and secondary alteration
(including biodegradation and water washing) and can lose their original
significance. Less attention has been paid to the application of REE to the
petroleum system.
• The newly found Aer Sag, located on the northeast margin of the Erlian Basin, first
produced commercial oil in 2006. It is a NE trending half-graben, covering an area
of 2000 km2, with 800 km2 in China and the rest in Mongolia.
Methodology
This study analyzed organic extracts and their corresponding whole rock materials for
REE compositions by inductively coupled plasma–mass spectrometry (ICP–MS).
Twenty-one samples were collected from the Lower Cretaceous of the Aer Sag, Erlian
Basin, northern China, including 14 mudstone samples and 7 oil sand
Case Study Four (cont.)
a, Crude oils from Well YM2 and Well TD2
sourced from the Middle-Upper Ordovician and
Cambrian marine source rocks, respectively are
regarded as two end-member oils in the Tarim
Basin, China (Jiao et al., 2010). TD2 crude oil
became denser by thermal alteration, with a
density
of 1.0217 g/cm3 1010 falling into the category
of heavy oil (Xiao et al., 2004).
b , Mississippian crude oils from Kansas State
and Anadarko Basin, USA sourced from
Devonian
Woodford (Chattanooga) shale enriched in
marine organic matter (Ramirez-Caro, 2013;
McIntire, 2014; 1013 Kwasny, 2015).
c , Dushanzi oil seeps from southern margin of
Junggar Basin mainly derived from Paleogene
lacustrine source rocks (Clayton et al., 1997; Li
et al., 2013).
d , Organic extract samples of marine
influenced coals from China can represent
transitional oil.
e , Niger delta crude oils with substantial
terrestrial organic matter input can represent
terrestrial oil (Akinlua et al., 2008).
Case Study Four (cont.)
a, Crude oils from Well YM2 and Well TD2 sourced from the Middle-Upper
Ordovician and
Cambrian marine source rocks, respectively are regarded as two end-member
oils in the Tarim
Basin, China (Jiao et al., 2010). TD2 crude oil became denser by thermal
alteration, with a density
of 1.0217 g/cm3 1010 falling into the category of heavy oil (Xiao et al., 2004).
b , Mississippian crude oils from Kansas State and Anadarko Basin, USA
sourced from Devonian
Woodford (Chattanooga) shale enriched in marine organic matter (Ramirez-
Caro, 2013; McIntire, 2014; 1013 Kwasny, 2015).
c , Dushanzi oil seeps from southern margin of Junggar Basin mainly derived
from Paleogene
lacustrine source rocks (Clayton et al., 1997; Li et al., 2013).
d , Organic extract samples of marine influenced coals from China can
represent transitional oil.
e , Niger delta crude oils with substantial terrestrial organic matter input can
represent terrestrial oil (Akinlua et al., 2008).
Case Study Four (cont.)
Fig. 1. PAAS normalized plots of the rare earth elements in various types of oils or extracts
from the world. REE patterns are plotted according to median values of available data.
Case Study Four (cont.)
Fig. 2. Cross-plot of REE values against the LaN/YbN ratio of various types of oils
or extracts from around the world
Summary of Case study four
• An attempt was made using rare earth elements (REE) for oil-source correlation
• REE cannot be used alone for oil-oil and/or oil-source correlations. Oil-source
correlations using REE were not consistent with conclusions based on biomarker
data and trace element ratios. Only one pair of oil-source rock relationships was
successfully established using REE.
CONCLUSION
REEs can be of Primary origin (Carbonatites, Alkaline igneous rocks, Iron-REE,
Hydrothermal veins and Stockworks) or Secondary origin (Laterites, Marine,
Alluvial and Paleo-placers).