QUEENSLAND UNIVERSITY OF TECHNOLOGY

SCHOOL OF PHYSICAL AND

CHEMICAL SCIENCES

Radiological Aspects of Petroleum Exploration

and Production in the Sultanate of Oman

Afkar Nadhim Al-Farsi

BSc (Hons), PGDip, MSc

A thesis submitted in partial fulfilment of the requirements of the degree of

Doctor of Philosophy

2008
 Dedicated to my mother Sheikha Issa, and

To my late grant parents Jokha Ali and Issa Said

i
Key words

NORM, radiological, petroleum, mining, dating, sludge farming, separation

tanks, radium, thorium, radon, lead-210, actinium, potassium, gamma
spectroscopy, gamma dose rate, 222Rn exhalation, sludge, oil scales, gas scales,
evaporation pond sediment, ambient soil, Oman

ii
Abstract

This thesis is a study of naturally occurring radioactive materials (NORM)

activity concentration, gamma dose rate and radon (222Rn) exhalation from the

waste streams of large-scale onshore petroleum operations. Types of activities

covered included; sludge recovery from separation tanks, sludge farming,

NORM storage, scaling in oil tubulars, scaling in gas production and

sedimentation in produced water evaporation ponds. Field work was conducted

in the arid desert terrain of an operational oil exploration and production region

in the Sultanate of Oman.

The main radionuclides found were 226Ra and 210Pb (238U - series), 228Ra and
228
Th (232Th - series), and 227
Ac (235U - series), along with 40
K. All activity

concentrations were higher than the ambient soil level and varied over several

orders of magnitude. The range of gamma dose rates at a 1 m height above

ground for the farm treated sludge had a range of 0.06-0.43 µSv h-1, and an

average close to the ambient soil mean of 0.086 ± 0.014 µSv h-1, whereas the

untreated sludge gamma dose rates had a range of 0.07-1.78 µSv h-1, and a mean

of 0.456 ± 0.303 µSv h-1. The geometric mean of ambient soil 222
Rn exhalation

rate for area surrounding the sludge was 3.1 19..07 mBq m-2 s-1. Radon exhalation

rates reported in oil waste products were all higher than the ambient soil value

and varied over three orders of magnitude.

iii
 This study resulted in some unique findings including: (i) detection of
227
radiotoxic Ac in the oil scales and sludge, (ii) need of a new empirical

relation between petroleum sludge activity concentrations and gamma dose

222
rates, and (iii) assessment of exhalation of Rn from oil sludge. Additionally

the study investigated a method to determine oil scale and sludge age by the use
228
of inherent behaviour of radionuclides as Ra:226Ra and 228
Th:228Ra activity

ratios.

iv
Contents
Key words .................................................................................................................................... ii

Abstract .......................................................................................................................................iii

Contents ....................................................................................................................................... v

List of Figures ...........................................................................................................................viii

List of Tables ............................................................................................................................... x

Statement of original authorship ............................................................................................. xii

Acknowledgements ...................................................................................................................xiii

CHAPTER 1 INTRODUCTION ............................................................ 1

1.1 Origin of petroleum ...................................................................................................... 1

1.2 History of NORM in the petroleum industry ............................................................. 2

1.3 Distribution of radioactivity in the petroleum exploration and production

processes ........................................................................................................................ 3

1.4 Onshore operations ..................................................................................................... 11

1.5 Gaps in knowledge ...................................................................................................... 15

CHAPTER 2 LOCALITY AND OIL MINING ...................................... 17

2.1 The Sultanate of Oman ............................................................................................... 17

2.2 Mining sites .................................................................................................................. 18

2.3 The surrounding area ................................................................................................. 20

2.4 The oil mining process ................................................................................................ 21

2.5 Implications of Oman’s aging reservoirs .................................................................. 22

2.6 The future of oil exploration in Oman ...................................................................... 24

CHAPTER 3 SAMPLING AND MEASUREMENT TECHNIQUES .... 27

3.1 Introduction ................................................................................................................. 27

3.2 Dating of petroleum scale and sludge ........................................................................ 28

3.3 In-situ gamma spectroscopy ....................................................................................... 30

3.4 Laboratory gamma spectroscopy .............................................................................. 32

3.4.1 Sample collection and preparation ........................................................................... 32
3.4.2 Gamma spectroscopy measurement procedure ........................................................ 34

v
3.5 Comparison between in-situ and laboratory gamma spectroscopy measurements ..
...................................................................................................................................... 37

3.6 In-situ gamma dose-rate measurements ................................................................... 40

3.7 Radon activity flux measurements using charcoal cups .......................................... 41

3.8 Radon exhalation rate measurements using the emanometer ................................. 43

CHAPTER 4 RADIOACTIVITY CONCENTRATION OF SCALE,

SLUDGE AND SOIL SEDIMENT, FROM THE OIL FIELDS OF THE
SOUTHERN OMAN DIRECTORATE.................................................... 47
4.1 Introduction ................................................................................................................. 47

4.2 Radioactivity in sludge................................................................................................ 48

4.2.1 Sludge farming ......................................................................................................... 49
4.2.2 Radioactivity in ambient soil.................................................................................... 53
4.2.3 Radioactivity in the sludge recovered from a separator tank ................................... 55
4.2.4 Radioactivity in untreated piles at sludge farms ....................................................... 58
4.2.5 Radioactivity in treated sludge strips ....................................................................... 68

4.3 Bahja NORM store yard ............................................................................................ 76

4.3.1 Oil industry scales .................................................................................................... 78
4.3.1.1 Oil scale formation and removal ..................................................................... 78
4.3.1.2 Radioactivity in oil scales ............................................................................... 81
4.3.2 Gas industry scales ................................................................................................... 87
4.3.2.1 Gas scale formation and removal.................................................................... 87
4.3.2.2 Radioactivity in gas scales .............................................................................. 88
4.3.3 Comparison between oil and gas scales ................................................................... 91
4.3.4 Radioactivity in the sludge stored in barrels ............................................................ 92

4.4 Radioactivity in the sediments of Al-Noor evaporation ponds ................................ 96

4.5 Discussion and conclusions ....................................................................................... 100

CHAPTER 5 GAMMA DOSE RATES AT SLUDGE FARMS IN

OILFIELDS OF THE SOUTHERN OMAN DIRECTORATE ................ 105
5.1 Introduction ............................................................................................................... 105

5.2 Terrestrial and cosmic gamma dose rates............................................................... 105

5.2.1 Gamma dose rates in the petroleum industry ......................................................... 109

5.3 Materials and Methods ............................................................................................. 111

5.4 Results and discussion .............................................................................................. 112

5.4.1 Correlation between measured and predicted gamma dose rate ............................. 112
5.4.2 Development of a new gamma dose rate empirical model ..................................... 113
5.4.3 Gamma dose rate measurements ............................................................................ 117
5.4.4 Combining synthesised and measured gamma dose rates ...................................... 127

5.5 Conclusions ................................................................................................................ 130

vi
CHAPTER 6 RADON-222 EXHALATION FROM PETROLEUM
INDUSTRY SCALE, SLUDGE AND SEDIMENT ................................ 133
6.1 Introduction ............................................................................................................... 133

6.2 Materials and methods ............................................................................................. 137

6.3 Results and discussion .............................................................................................. 138

6.3.1 Rn-222 exhalation rates .......................................................................................... 138

6.4 Conclusions ................................................................................................................ 153

CHAPTER 7 SUMMARY AND CONCLUSIONS ............................. 155

7.1 Summary.................................................................................................................... 155

7.2 Future directions ....................................................................................................... 167

References ................................................................................................................................ 170

vii
 List of Figures
Figure 1.1 Schematic on the precipitation of scales and sludge in production plant
and equipment where T: tubular, V: valves, W: wellheads, P: pumps, S:
separation tank, H: water treatment vessel, G: gas treatment, O: oil storage
tank ........................................................................................................................ 4
Figure 1.2 Primordial radioactive decay series (a) 238U, (b) 232Th and (c) 235U ........ 7
Figure 1.3 Produced water disposal in shallow, deep and producing reservoir wells
.............................................................................................................................. 10
Figure 1.4 Map of the Sultanate of Oman with Petroleum Development Oman’s
concession land ................................................................................................... 12
Figure 2.1 The five major oilfields studied during this research, all located within
PDO’s Southern Oman Directorate .................................................................. 19
Figure 2.2 Typical bedew rooming on their camels (picture courtesy of Trek Earth
http://www.trekearth.com/gallery/Middle_East/Oman/page19.htm) ............ 20
Figure 2.3 Daily oil, condensate and gas production in Oman over the last 11
years. .................................................................................................................... 23
Figure 3.1 The relative activity ratio of 228Th/228Ra and the relative decay of 228Ra
.............................................................................................................................. 29
Figure 3.2 (a) In situ gamma spectroscopy, and (b) A lead shield (designed and
poured at QUT) for shielding the NaI(Tl) probe of the portable gamma
spectroscopy system............................................................................................ 31
Figure 3.3 Correlation between field portable NaI(Tl) and laboratory HPGe
activity concentration readings for: (a) 226Ra Field vs 226Ra Lab, (b) 228Th Field vs
228
Th Lab, (c) 40K Field vs 40K Lab and (d) 228Th Field vs 228Ra Lab............................ 39
Figure 3.4 Charcoal cups planted on a sludge pile ................................................... 42
Figure 3.5 (a) Schematic diagram of the emanometer, and (b) The emanometer in
its wooden box housing ...................................................................................... 44
Figure 3.6 (a) Emanometer’s airtight PVC sample chambers with FESTO valves
and Perspex cover, and (b) a sludge sample wrapped in perforated textile
material, labelled and ready for 222Rn counting .............................................. 45
Figure 4.1 The sludge farming process: (a) sludge removed from a separation
tank, (b) untreated sludge piles, (c) sludge piles after transport to the farming
area, (d) a typical sludge strip, (e) watering the sludge strips, and (f) tilling
the sludge strips. ................................................................................................. 52
Figure 4.2: Relation between 228Ra:226Ra and 228Th:228Ra activity ratios............... 58
Figure 4.3: Relation between 226Ra and 228Ra for Marmul, Bahja and Nimr
untreated sludge piles. ........................................................................................ 65
Figure 4.4: 228Ra:226Ra and 228Th:228Ra mean activity ratios for Bahja, Nimr and
Marmul sludge farms. ........................................................................................ 66
Figure 4.5: Sludge pile activity concentration versus age (a) 226Ra, and (b) 228Ra. 67
Figure 4.6: NORM store yards: ................................................................................. 77
Figure 4.7: Average activity concentrations for radionuclides found in oil and gas
scales. ................................................................................................................... 92

viii
Figure 4.8: Section 2 of Al-Noor evaporation pond [picture courtesy of
Mohammad Al-Masri] ....................................................................................... 97
Figure 5.1 Relation between measured and predicted gamma dose rates using
UNSCEAR (2000) dose conversion factors. ................................................... 113
Figure 5.2 Relation between measured and empirically determined gamma dose
rates.................................................................................................................... 116
Figure 5.3 3D graph of gamma dose rate relation with both 226Ra and 228Ra
activity concentrations. .................................................................................... 126
Figure 5.4 Measured and predicted gamma dose rate profiles at a 1 m height for
untreated sludge piles and treated strips at Bahja, Nimr and Marmul sludge
farms (where n denotes the total number of samples at each location). ...... 128
Figure 6.1 Emanometer to charcoal cup readings correlation .............................. 139
Figure 6.2 222Rn exhalation rate versus 226Ra activity concentration ................... 144
Figure 6.3 222Rn exhalation rate range and averages for the various sample types
............................................................................................................................ 150
Figure 6.4 Ratio of 222Rn exhalation rate to 226Ra activity concentration range and
averages for the various sample types ............................................................ 151

ix
 List of Tables
Table 1.1 Typical 226Ra and 228Ra activity concentrations for various primary
production and power generation industries according to APPEA activity
concentrations (kBq kg-1) .................................................................................. 14
Table 4.1: Bahja, Nimr and Marmul sludge farm locations, estimated volume of
untreated sludge in piles and number of treated sludge Strips at the time of
this study (Jan 2006 – June 2007) ..................................................................... 50
Table 4.2: Activity concentration (Bq kg-1) for ambient soils of Bahja, Al-Noor,
Nimr and Marmul and the world average (UNSCEAR, 2000) (uncertainties
represent counting error)................................................................................... 54
Table 4.3: Activity concentration (Bq kg-1) and individual reading error of freshly
removed sludge from a Nimr station separator tank ...................................... 56
Table 4.4: Sludge activity concentrations (Bq kg-1) and radioisotope ratios from
Bahja, Nimr and Marmul untreated sludge piles ............................................ 60
Table 4.5: Activity concentrations (Bq kg-1) of untreated Bahja sludge piles........ 61
Table 4.6 Activity concentrations (Bq kg-1) of untreated Nimr sludge piles
(analysed using the HPGe gamma spectroscopy system). ............................... 63
Table 4.7 Activity concentrations (Bq kg-1) of untreated Marmul sludge piles
(using the HPGe gamma spectroscopy system). .............................................. 64
Table 4.8 Activity concentration (Bq kg-1) of Bahja sludge strips. ......................... 71
Table 4.9 Activity concentrations (Bq kg-1) of Nimr sludge strips. ......................... 72
Table 4.10 Activity concentrations (Bq kg-1) of Marmul sludge strips. .................. 74
Table 4.11 Committed effective dose coefficients (µSv Bq-1) of selected
radionuclides likely to be present in petroleum scales (ICRP68) ................... 84
Table 4.12 Activity concentrations (Bq kg-1) of oil scale samples. .......................... 86
Table 4.13 Activity concentrations (Bq kg-1) of gas scale samples. ......................... 90
Table 4.14 Range of sludge 226Ra and 228Ra activity concentrations (kBq kg-1) for
oil exploration operations of several countries of the world ........................... 94
Table 4.15 Activity concentrations (Bq kg-1) for sludge stored in barrels.............. 95
Table 4.16 Activity concentrations (Bq kg-1) of Al-Noor evaporation pond soil
sediments. ............................................................................................................ 99
Table 5.1 Air Kerma rate at 1 m height per disintegration rate (nGy h-1 per
Bq kg-1) of the parent nuclide per unit soil weight for natural sources
uniformly distributed in the ground (adapted from Saito and Jacob). ....... 108
Table 5.2 Measured gamma dose rates and 226Ra, 228Ra and 40K activity
concentrations for Bahja, Nimr and Marmul untreated sludge piles .......... 120
Table 5.3 Measured gamma dose rates and 226Ra, 228Ra and 40K activity
concentrations for Bahja, Nimr and Marmul treated sludge strips ............ 122
Table 5.4 Summary of field measured gamma dose rates (µSv h-1) at 1 m height
for Bahja, Nimr and Marmul petroleum sludge treatment farms’.............. 125

x
Table 5.5 Number of samples, mean, median and range of the dose rates for
untreated and treated sludge at Bahja, Nimr and Marmul obtained by both
direct measurement and empirical relation. .................................................. 129
Table 6.1(a): 222Rn exhalation rate, 226Ra activity concentration and 222Rn to 226Ra
ratio for various petroleum industry radioactive waste. ............................... 140
Table 6.1(b): 222Rn exhalation rate, 226Ra activity concentration and 222Rn to 226Ra
ratio for various petroleum industry radioactive waste (emanometer
measurements only). ......................................................................................... 142
Table 6.2: Arithmetic mean, geometric mean maximum and minimum 222Rn
exhalation rates, and arithmetic and geometric means of 222Rn:226Ra ratio for
the various samples........................................................................................... 148
Table 7.1 (a): Range median and mean activity concentrations of 226Ra, 210Pb,
228
Ra, 228Th, 227Ac and 40K in Bq kg-1, for the various sample types analysed in
this study ........................................................................................................... 159
Table 7.1 (b): Mean (± standard deviation), median and range of gamma dose
rates in µSv h-1 for untreated and treated sludge in Bahja, Nimr and Marmul
sludge farms, and ambient soil readings ........................................................ 162
Table 7.1 (c): Maximum, minimum and geometric mean of 222Rn exhalation rates
in mBq m-2 s-1 and the geometric mean of radon exhalation to radium
concentration ratio in mBq m-2 s-1/Bq kg-1 for the various sample types
analysed in this study ...................................................................................... 164

xi
Statement of original authorship

The work contained in this thesis has not been previously submitted for a degree
or a diploma at any other higher education institution. To the best of my
knowledge and belief, the thesis contains no materials previously published or
written by another person except where due reference is made.

Signature:

Date: 17 December 2008

xii
Acknowledgements
In the name of God, most Gracious, most Merciful. I initially would like to start
by thanking God for the gift of life and for empowering his powerless creatures
to realise (with hard work and dedication) their aspirations and dreams. Then I
would like to have the honour of mentioning in my humble thesis the name of
the greatest human being ever to walk on earth; “Mohammad” peace be upon
him, and use one of his wise quotes: “He does not thank Allah, who does not
thank people”.

The success in carrying out various aspects of this work would not have been
possible without the generous contributions in funding and volunteer support
provided by many people. My heartfelt appreciation is given to all the persons
involved. In the event of these acknowledgements failing to mention the names
of any particular person(s) or organisation(s), I offer my sincerest apologies.

I would like to thank Sultan Qaboos University for granting me the sabbatical to
embark on the doctorate research degree, and also for allowing me use of
Laboratory Instruments to analyse field collected samples of this research work.
I would like to thank Queensland Univesity of Technology (QUT) for granting
me the PhD Fee Waiver Scholarship, and for bearing the financial costs of the
research’s instruments purchase and development along with international
shipment between Brisbane (Australia) and Muscat (The Sultanate of Oman). I
also would like to extend my thanks to Petroleum Development Oman (PDO)
for the collaboration and logistic support during the research work, which
included air transportation to and from the petroleum mining sites, land
transportation within the mining sites, accommodation and meals. Not
forgetting the special transportation arrangements made for the instruments by a
cargo truck between Muscat and the desert mining locations.

QUT academics, professionals and fellow students: Special thanks and

gratitude are due to my principal supervisor: Dr. Riaz Akber for being my
mentor, for his guidance, patience, expert feedback and enthusiastic help and
support. Thanks are also due to my associate supervisor: Professor Lidia
Morawska for being my mentor, for her guidance and encouragement. I am truly
highly indebted to A/Professor Brian Thomas for his instrumental role in my
enrolment at QUT, continuous encouragement, advice, help and support
throughout my Master and Doctorate degrees. A lot of thanks are also due to my
Master degree principle supervisor: Dr David Thiele for being a great mentor
and bringing me up to the PhD degree doorstep. Thanks are also due to my
Master degree associate supervisor: Dr Gregory Michael for his expert advice
and support. Thanks and gratitude are also due to Ms. Rachael Robinson for the
professional proof reading and Ms. Kerry Kruger for the final styling
organisation of the thesis. Thanks are also due to the professional support of Mr.
Jaya Dharmasiri, Mr. John Barrett, Ms. Elizabeth Stein, Ms. Magaret
McBurney, Mr. Robert Organ and Mr. James Drysdale. I would also like to
thank all my fellow students for their friendship, support and sharing
educational experiences and especially: Hussein Kanaani, Yudi Wardoyo, Sade
Fatokun, Diane Keogh, Mohammad Al-Roumy, Ezzat Abu Azza and Javaid
Khan.

xiii
SQU academics and professionals: Many thanks are due to A/Professor Fadhil
Mahdi Saleh, for his advice and recommendations on my career planning and
development. Thanks are also due to Professor Lamk Al-Lamki, for his
continuous support, help and encouragement. Many thanks to my colleagues; Dr
Haddia Bererhi, Dr Nadir Atari, Mr Kirthi Jayasekara, Mr Hilal Al-Zheimi,
Mr Mohammad Al-Subhi, Mrs Fatma Al-Maskery, Mrs Ibtisam Al-Maskery
and Mrs Amaal Al-Rasby for their support and understanding with sharing the
department’s facilities during this study’s sample analysis work.

PDO professionals: Many thanks are due to Mr. Naaman Al-Naamany,

Mr. Brett Young, Mr. Ahmed Al-Sabahi for their logistic support of the project
and planning, providing transportation, accommodation and meals during the
field work. The list of names for the people who offered volunteer help during
the field work visits on the different locations is too long; to name a few:
Mr. Said Saud Al-Maawaly, Mr. Salim Al-Rawahy, Mr. Nasser Abdullah
Al-Kitany, Mr. Rashid Said Shinoun, Mr. Salim Al-Riyami, Mr. Rashid
Al-Zakwani, Mr. Ahmed Al-Jabri and Mr. Seif Al-Habsy. To all the above and
the others, I would like to say thank you for your help and support during the
field visits.

Other professionals: Many thanks are also due to Professor Mohammad

Al Masri (Syrian Atomic Energy Agency) for advice and academic enrichment
on the study during the field work, and collection of the sediment samples.
Thanks are also due to Mr. Gert Jonkers (Shell Company) for providing us with
bibliography on petroleum industry NORM. I would also like to thank Mr.
Ibrahim Awad for his advice and help during sample collection.

Family and friends: Thanks are also due to all my friends. Special thanks to all
my family members for their support and encouragement. Finally, I would like
to offer my sincere appreciation to my beloved wife: Ahlam Al-Adawi, for her
relentless support, encouragement and sacrifice through this ostensibly jam-pact
period of our lives.

xiv
Chapter 1 INTRODUCTION

1.1 Origin of petroleum

There are currently two plausible scientific theories that explain the process

of oil formation. The first is the biotic or biogenic theory, which states that oil

was formed hundreds of millions of years ago, following the extinction of

dinosaurs (i.e. terrestrial reptiles of the Mesozoic era) and algae that inhabited

the earth some 65-248 million years ago. The remaining organic matter was

then buried under many layers of sediment, and was exposed to high levels of

litho-spherical heat and pressure, which then transformed this preserved matter

into hydrocarbons (black gold or oil). According to geologists, this process is

thought to occur amid the earth’s solid rock layers, at temperatures ranging from

80-350 °C and pressures ranging from 0.8-2 kbar (Dyer and Graham, 2002,

Dutkiewicz et al., 2003). The oil then migrates and remains in porous stones

(such as limestone or sandstone, which have a porosity of about 20%) until it is

discovered.

The second theory is known as the abiotic or abiogenic theory, which states

that oil is not a fossil fuel, but that it was formed from inorganic materials deep

within the earth’s crust. According to this theory, hydrogen and carbon

molecules found in the earth’s mantle are subject to extremely high

temperatures and pressures, causing them to form hydrocarbon molecules,

which then migrate upward into oil reservoirs, through deep fracture networks

in the earth’s crust. Supporters of the abiogenic theory claim that the millions of

barrels of oil produced per day (1 barrel = 159 L) could not possibly be supplied

1
by the limited number of pre-historic animals (algae and dinosaurs) that existed.

For example, according to Morton (2004), the most productive oil well in Saudi

Arabia (Al-Ghawar) produces about 5x106 barrels of crude oil per day, with a

cumulative production of 5.5x1010 barrels of crude oil since 1951. Although

there is support for both theories, no one is mutually exclusive from the other,

and both may be equally as valid.

1.2 History of NORM in the petroleum industry

Kolb and Wojcik (1985) provide an interesting account of the discovery of

naturally occurring radioactive materials (NORM) in petroleum. The presence

of higher than background concentrations of radioactivity in crude petroleum

was reported for the first time more than a century ago, by Himstedt (1904) and

Burton (1904). In the 1920-1930’s, the presence of NORM was also reported in

numerous Russian and German research papers, however the first official

survey, from a radiation protection point of view, was not done until the early

1970’s.

Subsequent to the detection of NORM in a North Sea oil platform in 1981,

the presence of NORM in crude petroleum and petroleum industry waste has

been studied and reported by a number of authors worldwide, including Kolb

and Wajcik (1985), Smith (1987), Wilson and Scott (1992), Heaton and

Lambley (1995), Paschoa (1997), White and Rood (2001), Matta et al. (2002),

Godoy and Petinatti da Cruz (2003), Hamlat et al. (2003a), Hamlat et al.

(2003b), Smith et al. (2003), Al-Masri and Aba (2005) and Gazineu and Hazin

(2007).

2
 In the petroleum industry, naturally occurring radionuclide concentrations

are often enhanced as a result of industrial operations. Whilst these materials are

formally referred to as technologically enhanced NORM (TENORM), the term

NORM is more widely used in both industry and the literature.

Examples of other industrial operations that have NORM present in their

primary material, products, by-products and waste include: uranium mining and

milling, metal mining and smelting, phosphate industries, coal mining and

power generation from coal, rare earth and titanium oxide industries, zirconium

and ceramics industries, building material disposal and the application of natural

radionuclides, such as radium and thorium. Whilst the activity levels of these

NORM are not always enhanced, simple chemical or physical changes can

sometimes take place, resulting in the radionuclides being more readily

available for transfer by various pathways (Heaton and Lambley, 1995,

UNSCEAR, 2001). For example, in uranium mining, simply bringing the

uranium to the surface can often leave radionuclide tailings, that may pose a

radiological threat to both the environment and the general public.

1.3 Distribution of radioactivity in the petroleum

exploration and production processes
During the process of oil exploration and production (E&P), radioactive by-

products, such as scale and sludge, are formed and retained in the processing

equipment (Figure 1.1). Scales are formed in the electric submersible pumps,

down-hole tubular, upstream tubular and well heads (Testa et al., 1994, Al-

Masri and Aba, 2005, Othman et al., 2005), while its brittle nature can also

3
cause it to dislodge from the pipe walls and migrate to the oil-water separation

tanks.

Sludge, on the other hand, is found in the downstream tubular, water-oil

separation vessels, slops tanks of oil production facilities and storage tanks, and

as a result of the processes of tubular cleaning using ‘pig’ devices. It contains a

mixture of hydrocarbon, mud, natural radionuclides, sediments, bacterial

growth, corrosion particles and some scale debris (APPEA, 2002, Omar et al.,

2004). While the activity of radium in sludge is generally lower than that found

in scale (Vandenhove, 2002), it has still been found to be significantly above

background levels.

210
Pb film

Upstream Downstream
G
P
W

V S O

Sludge H
Scale

Formation water,
oil and gas

Figure 1.1: Schematic on the precipitation of scales and sludge in production plant
and equipment where T: tubular, V: valves, W: wellheads, P: pumps, S:
separation tank, H: water treatment vessel, G: gas treatment, O: oil storage tank.

4
 The estimated annual radium activity brought to the surface by global oil

exploration is in the order of 10 TBq (Lieser, 1995). This not only poses

significant health risks to the industry workers, but also to the community and

environment as a whole. In the United States, they are spending about

US$ 6 billion per year on the clean up and containment of such radioactive

waste (Harley, 2000).

238
The NORM found in scale and sludge are mainly from the U (T½: 4.5
232
billion years) and Th (T½: 14 billion years) natural radioactive decay series
235
(Figures 1.2 (a) and (b)). In contrast, Ac-227 (T½: 21.77 years) from the U

(T½: 0.7 billion years) natural radioactive decay series (Figure 1.2 (c)) was

detected for the first time during this research, and prior to this, it was only ever

mentioned in passing by Kolb and Wajcik (1985). The main isotopes found in

scale and sludge are those of 226Ra (T½: 1602 years; 238U primordial series), and
228 232
to a lesser degree Ra (T½: 5.75 years; Th primordial series). These two

radium isotopes are present as both sulphates and carbonates in the strontium,

barium and calcium mineral scales that develop in the tubular and other areas of

the extraction rigs (Wilson and Scott, 1992, Hamlat et al., 2001, Godoy and

Petinatti da Cruz, 2003, Al-Masri and Aba, 2005).

In the petroleum reservoirs, crude oil co-exists with underground water,

usually called ‘formation water’ or ‘formation brine’. While the initial oil

production process is usually dry (Smith, 1987), as the reservoir pressure falls

over time, water can also be co-produced with the crude oil, and this water is

given the name ‘produced water’. The amount of NORM formed in oil

5
producing fields and incorporated into the scale and sludge, is directly

proportional to the volume of produced water generated during the pumping of

the oil (Rood et al., 1998, Paranhos Gazineu et al., 2005).

238 234
U U (a)
β1.2 minutes
α 4.5 billion
years 234 α 240 years
β 24 days Pa
234 230
Th Th
α 77,000 years

226 Leach from reservoir

Ra
rock into formation water
α 1,602 years

Transported with 222

Rn
natural gas
α 3.8 days

218 214 210

Po Po β Po
α β
20 minutesα 160 micro-seconds
3.1 minutes 5 days
α 140 days
214 210
Bi Bi
β 27 minutes β 22.3 years
214 210 206
Pb Pb Pb

Precipitate on internal surfaces

of petroleum equipment

6
 (b)
228
β
232
Th Th
14 6.1 hours
α billion β
228
Ac α 1.9 years
years
5.75 years
228 224
Ra Ra
α 3.7 days
Leach from reservoir 220
Transported with
rock into formation water Rn natural gas
α 56 seconds

216 212
Po β Po
α 61 minutes
(64%) α seconds
0.15 seconds 310 nano-
212
Bi
β 11 hours
212 α 61 minutes
(36%) β 208
Pb Pb
3.1 minutes
208
Tl
Precipitate on internal
surfaces of petroleum
equipment

235
U (c)
α 700
million
years
β 231
Pa
26 hours
231
Th α 33,000
β
227
Th
years

227
22 years
(99%) α 19 days
Ac
Detected in α 22
β
223
oil and gas years Ra
(1%)
scales 223
22 minutes
α 11 days
Fr
219
Rn
α 4 seconds

215
Po
α 1.8 milliseconds 211
Bi
β
36 minutes
211
Pb
α 2.1 minutes 207
Pb
β 4.8 minutes
207
Tl

Figure 1.2: Primordial radioactive decay series (a) 238U, (b) 232Th and (c) 235U.

7
 226 228 224
The major radionuclides found in produced water include Ra, Ra, Ra
210
and Pb, in concentrations of up to a few hundred becquerels per litre (IAEA,

2003). This is because radium isotopes leach into the oil reservoir, as a result of

their high solubility in water, when compared to uranium and thorium. The high

temperature and pressure in the oil reservoirs also aid in the leaching of radium

from reservoir rock into the formation water. Because geological formations are

not always closed, this may allow 226Ra to migrate into the soil matrix and deposit

elsewhere outside the formation. If this takes place, the secular equilibrium of
226
Ra with its parent will no longer exist, and the radium is then said to be

“unsupported”, meaning that its activity is not related to the activity of its series

predecessors (Paranhos Gazineu et al., 2005).

The produced water associated with the explored oil is usually saline,

containing potentially high levels of mineral salts, such as sodium chloride

(NaCl). They contain not only elements of low potential toxicity (Na, K, Ca, Ba,

Sr and Mg), but also more toxic elements, such as Pb, Zn, Cd and Hg. Other

minerals that may be present in the produced water include traces of oil, metals

and noxious gases. The reported salinities of produced water vary from 1-

400 g L-1 (USGS, 1997). For comparison, seawater has a salinity of around

35 g L-1 (USGS, 1997). The United States Environmental Protection Agency

(USEPA, 2005), Australia’s National Health and Medical Research Council

(NHMRC, 1996), and the World Heath Organisation (WHO, 2004) all

recommended that the level of salinity or total dissolved solids (TDS) in safe

drinking water should be less than 0.5 g L-1, though up to 1 g L-1 is palatable.

8
 The salinity of the produced water may increase over the production lifetime

of an oil well, suggesting the co-production of brine. As such, the dissolution of

radium and other group II elements from the formation rock may be enhanced by

the higher salinity of the produced water, in a manner similar to that which occurs

as a result of injecting seawater to enhance recovery. This indicates that NORMs

may be absent at the start of production, but may appear in the later stages of the

well’s lifetime. The quantities of scale and sludge produced vary significantly

between reservoirs, individual wells and production conditions. Therefore, there

is no typical radionuclide concentration in NORMs from oil and gas production,

nor is there a typical quantity of scale and sludge produced annually or over the

lifetime of an oil well.

Petroleum companies have several management options with regard to the

produced water, after it has been separated from the crude oil. These include,

injection of the produced water into deep abandoned oil wells, pumping it into

evaporation ponds, or injecting it back into reservoirs to aid in the recovery of

more crude oil (Figure 1.3). The shallow disposal management option has been

consistently reduced in order to minimise produced water surface environmental

impact.

9
 152 122
Volume (million of barrels)

312 276 217

385

645 732
575 Shallow disposal
550 547
497 Deep disposal
Producing resevoir

696 730 764 733

621 674

02 03 04 05 06 07

Year

Figure 1.3: Produced water disposal in shallow, deep and producing reservoir
wells.

Another alternative was also found when a new technology called “Solar

Dew” was introduced by Petroleum Development Oman (PDO), designed to

purify the produced water. This system purifies water using a solar-driven, non-

porous membrane distillation process. Water purified using this process passes

World Health Organisation (WHO) and Oman standards for drinking water.

However, it does require the addition of a number of minerals before it is deemed

adequate for human consumption. A desert greening project has also been

successfully launched in Oman using solar dew purified water for irrigation

(PDO, 2001).

10
1.4 Onshore operations
Oman discovered oil in 1962, and the first oil export consignment took place

in 1967. Oil is the country’s major source of income; it comprises 80% of the

export income, and 40% of the Gross Domestic Product (GDP). To date, the

largest oil producing company in Oman, Petroleum Development Oman (PDO),

has only been undertaking onshore oil exploration and production. It produces

90% of the country’s crude oil and almost all of the country’s natural gas.

PDO’s major shareholders are: the Oman Government (60%), Royal Dutch

Shell (34%), Total (4%) and Partex (2%).

The facilities operated by PDO cover approximately 114,000 km2 of

concession land (PDO, 2001), and the Oman government has granted PDO the

use of this land (Figure 1.4) for oil and gas exploration until 2044. Within this

area, PDO executes a range of activities, such as seismic surveys, drilling and

production. The area comprises 120 producing oil fields, 3,750 producing wells,

59 gathering and production stations and over 7,000 km of pipes and flow lines,

and these operations invariably create localised disturbances within the

environment.

11
Figure 1.4: Map of the Sultanate of Oman with Petroleum Development Oman’s
concession land.

12
 An internal PDO inventory of oily waste, conducted in 2001, revealed that it

has in excess of 100,000 tonnes of oily sand/sludge, stored at 8 waste

management centres in the county’s interior regions, and a further 30,000 tonnes

was being treated at the time (PDO, 2001). These sludge volumes would have

substantially increased since then, due to the fact that an estimated 72,000

tonnes of oily sludge are produced annually (Al-Futaisi et al., 2007).

At PDO, one of the major issues they face is the handling of radioactive

sludge material and its eventual disposal. As mentioned earlier, the sludge

contains radioactivity, mainly due to radioisotopes of radium (226Ra and 228Ra).

As radium isotopes and their progeny are strong gamma emitters, the external

radiation dose in the vicinity of separation tanks increases as sludge builds up.

Moreover, frequent cleaning and replacing the lining of these tanks further

increases the external radiation dose. This work is generally carried out by

personnel accessing the interior of the tank, and because of the confined
222 220
environment within the tank, Rn and Rn tend to build up, leading to

significant air concentrations of hazardous radioactive material.

Petroleum industry sludge disposal methods are similar to those used to

dispose of tailings from the mining and milling of uranium ores. The average

ore grade at Roxby and ERA Ranger uranium mines in Australia are such that
226
the Ra activity concentrations in their tailing repositories are expected to be

6.6 and 31 kBq kg-1, respectively (Sonter et al., 2002). These values are

comparable to the PDO sludge activity concentration range of 0.15-1 kBq kg-1

(Salih et al., 2005). The Australian Petroleum Production and Exploration

13
Association (APPEA, 2002) also reported similar activity concentrations of
228 226
Ra and Ra found in the NORMs of primary production and power

generation industries (Table 1.1).

Table 1.1: Typical 226Ra and 228Ra activity concentrations for various primary
production and power generation industries according to APPEA activity
concentrations (kBq kg-1)
228 226
Material/Grade Ra Ra

Uranium ore (1% U) - 120

Monazite 200 – 290 1.2 – 37

Xenotime 61 48

Fly ash 0.56 0.56

Phosphate rocks 4.8 0.12

226
To date in Oman, sludge with Ra activity concentrations > 1 kBq kg-1 is

contained in barrels, which are temporarily stored in confined concrete fenced

areas. The more oily sludge is stored in recently engineered hold up ponds

(100 x 10 x 1 m), lined with special geo-textile material. However, the issue of

long-term disposal of sludge remains and current methods need to be thoroughly

evaluated in order to ascertain their merits and demerits. On the other hand,

sludge with 226Ra activity concentration < 1 kBq kg-1 undergoes sludge farming

process.

The removal of scale from NORM contaminated tubular also generates

radioactive waste. This is commonly done by human operated machines that use

mechanical arms and pneumatic pressure to scrape and blow away the scale

14
from the inner surface of the pipes. However, significant amounts of dust are

also suspended during this process, resulting in the inhalation and ingestion of

radioactive particles by personnel. The total radiation dose can then be derived

from the internal dose exposure pathways and the external dose pathways.

PDO has thousands of NORM contaminated tubular and processing pieces of

equipment that require the scale removal process. This de-scaling project is still

under review by PDO’s Health, Safety and Environment (HSE) department.

1.5 Gaps in knowledge

Studies of NORM enhancement in the scale, sludge and produced water of

typical petroleum industries have been conducted in the past (Kolb and Wojcik,

1985, Heaton and Lambley, 1995, Paschoa, 1997, Spitz et al., 1997, Shawky et

al., 2001, White and Rood, 2001, Jerez Veguería et al., 2002, Paschoa and

Godoy, 2002, Al-Masri, 2006), however, most of these studies focus on the

offshore exploration and production operations conducted in the North Sea and

Brazil. According to an assessment reported by the European Commission

(Oman, 2008), the petroleum industry now contributes more radioactivity to the

North Sea than the nuclear power industry, which includes numerous power

stations and processing plants.

The main objective of this research project is to conduct a comprehensive

assessment and evaluation of the activity concentration and gamma dose rate of

large-scale onshore petroleum operations in ‘the Sultanate of Oman’. To the

best of our knowledge, no comprehensive and systematic studies on the

radiological impact of the industry have ever been carried out, particularly in the

15
Middle East and the Gulf region, which is the largest producer of oil worldwide.

This research also investigates radon gas exhalation from petroleum treated and

untreated sludge, oil and gas scales samples, and from evaporation pond

sediment soils. This assessment of radon gas exhalation in the petroleum

industry is the first of its kind; however it is somewhat limited in scope, due to

the fact that access permits were only granted to a limited number of sites in the

area.

16
Chapter 2 LOCALITY AND OIL MINING

2.1 The Sultanate of Oman

The Sultanate of Oman is one of six oil producing countries that make up the

Gulf Cooperation Council (GCC). These countries include the Sultanate of Oman,

the Kingdom of Saudi Arabia, the Kingdom of Bahrain, the United Arab

Emirates, Qatar and Kuwait. Oman is situated in the south eastern corner of the

Middle East (Arabian Peninsula), located between latitudes 16.40-26.20°N and

longitudes 51.50-59.40°E. It has an area of 309,500 km2 and a population of

2.6 million (Oman, 2008). It is bordered by the United Arab Emirates to the

northwest, the Kingdom of Saudi Arabia to the west and the Republic of Yemen

to the southwest. Oman also has a coast line of approximately 1700 km, adjoining

the Oman Gulf along its north eastern boarder and the Arabian Sea to the south

east. The capital, Muscat, is located on the country’s north eastern border, near

the Tropic of Cancer.

To date, the largest oil producing company in Oman, ‘Petroleum

Development Oman (PDO)’, produces 90% of the country’s crude oil and almost

all of the country’s natural gas. In 2006, a workforce of 5,000 people were

managing and handing the oil mining process at PDO (PDO, 2006).

17
2.2 Mining sites
PDO have divided their operations into two regions, otherwise known as the

“Northern Oman Directorate (NOD)” and the “Southern Oman Directorate

(SOD)”. The NOD accounts for half of PDO’s production and it contains four

clusters of oil fields, namely the Lekwair, Fahud, Yibal and Qarn Alam clusters.

The SOD accounts for the other half of production and it contains five clusters,

namely the Bahja, Marmul, Nimr, Harweel and Rahab Thuleilat Qaharir (RTQ)

clusters. The major oilfields studied during this research included Al Noor,

Bahja, Marmul, Nimr and Zuliya, which were all located within PDO’s SOD

(see Figure 2.1).

18
Figure 2.1: The five major oilfields studied during this research, all located within
PDO’s Southern Oman Directorate.

19
2.3 The surrounding area
Inhabitants from the surrounding areas are predominantly bedews

(shepherds), who traditionally moved around with their herds of sheep and

camels to wherever water and food could be found (Figure 2.2). However, a

recent shift towards a more semi-urban lifestyle has seen many bedews

beginning to settle in permanent wooden or concrete houses. And in addition to

relying on their livestock for food, they are now beginning to rely on the

increasing number of grocery stores that have opened up in scattered locations

throughout the local area.

This image is not available online.

Please consult the hardcopy thesis
available from the QUT Library

Figure 2.2: Typical bedew rooming on their camels (picture courtesy of Trek
Earth http://www.trekearth.com/gallery/Middle_East/Oman/page19.htm).

These newly established residential areas are located in close proximity

(within 10km) to the sludge farms of Bahja, Nimr and Marmul, as well as the

20
Bahja NORM store yard. These facilities are surrounded by wire mesh boundary

fences, with guarded gates, in order to ensure that the local community, and

straying animals, are kept out of these contaminated areas.

2.4 The oil mining process

Oil mining can be divided into four major phases: exploration, drilling,

production, and rehabilitation and restoration. In the exploration phase, seismic

waves are used to detect the presence of underground hydrocarbons in the

surrounding area. Rock samples are also taken for laboratory analysis and

exploration wells are then drilled, in order to confirm the existence of oil

reservoirs. Once the presence of oil has been confirmed, the drilling of production

wells can then commence. This drilling process is a precise science, which can be

expensive and extremely hazardous, since many oil and gas reservoirs exist at

very high temperatures and pressures, ranging from 80-350 °C and 0.8-2 kbar,

respectively (Dyer and Graham, 2002, Dutkiewicz et al., 2003).

Once the wells have been drilled, they are then secured and capped, before

finally being connected to a collection of valves called the wellhead. These valves

channel the flow of crude oil (which coexists with both saline produced water and

natural gas) from the reservoir into distribution pipelines. After travelling along

these pipelines, which can range from a few kilometres to tens of kilometres long,

the crude oil eventually reaches the gathering station, where it enters large

separation tanks (1200 m3) that allow for the crude oil, natural gas and produced

water to separate. The dehydrated, degassed crude oil is then pumped to Mina

Al-Fahal sea port in Muscat (which is up to 800 km from some gathering stations)

21
for export on large oil tankers. In contrast, the natural gas component is delivered

to a number of Oman Government agencies for local use, as well as to the Oman

and Qalhat Liquefied Natural Gas (LNG) plants, near Sur sea port, for export on

LNG transporting tankers. The produced water is dealt with in a number of ways

that have already been discussed in detail in Chapter 1.

2.5 Implications of Oman’s aging reservoirs

When oil flows to the surface naturally, as a result of its own reservoir

pressure, it is by far the most convenient and cost effective means of oil

extraction. However, when an oil well begins to age and the reservoir pressure

falls, it becomes necessary to use artificial methods of extraction, such as

electrical submerged pumps or beam pumps (nodding donkeys). In general,

petroleum companies only recover 30-40% of the oil contained in a given

reservoir using this method (Chierici, 1992, Carrero et al., 2007).

While the oil production process is essentially anhydrous, with time, and as

the reservoir pressure falls, produced water is often co-produced along with the

crude oil. Hence, as a well ages, the ratio of produced water to crude oil increases,

sometimes reaching as high as 95% of the total production volume, while still

remaining economically viable (Oil & Gas_UK, 2008).

In 2002, PDO produced 3.774 million barrels (6 x 105 m3) of produced water

per day, while its daily crude oil production was 0.849 million barrels

(1.35 x 105 m3) – a total produced water volume of 82%. However, by the end of

2006, PDO’s produced water had increased to 88% of the total production volume

22
 (PDO, 2006), indicating that PDO’s oil reservoirs may have already reached their

peak production capacities (see Figure 2.3).

1200
Gas
Condensate
Black oil
(thousands of barrels of oil equivalent)

900
Average daily production

600

300

0
97 98 99 00 01 02 03 04 05 06 07
Year

Figure 2.3: Daily oil, condensate and gas production in Oman over the last 11
years.

This problem of aging oil wells is not restricted only to Oman. In 1993, the

United States total annual produced water volume was 25 billion barrels

(4 x 109 m3), whereas the crude oil total volume was only 2.5 billion barrels

(4 x 108 m3) – a total produced water volume of 91%. In response to this global

problem, PDO have started to investigate the use of enhanced oil recovery (EOR)

technologies, which work by flooding the reservoir with substances such as: (i)

reinjected produced water; (ii) a special water/polymer mix; (iii) gas (otherwise

known as ‘gas lifting’); or (iv) steam, in order to force the remaining, more

viscous oil into adjacent producing wells.

23
 After flooding a well with reinjected produced water, the amount of

remaining oil may still be as high as 70% of the original oil volume, as the oil is

often too viscous and heavy to be moved by the water alone. However, the

addition of an alkaline surfactant polymer to the produced water, prior to

reinjecting it into the reservoir, increases the viscosity of the injected fluid and

increases the oil recovery factor, along with the final volume of oil produced

(Carrero et al., 2007).

Gas lifting, on the other hand, works by pumping natural gas into the

reservoir, which then mixes with the oil, making it less viscous and thus, more

mobile. Once the oil has been extracted, the gas is then recovered and reinjected

back to the reservoir to extract more oil. Similarly, injecting steam into the

reservoir also acts to decrease the viscosity of heavy oil, thus also increasing

yields.

Whilst the complete removal of oil from reservoirs is not possible with any of

the existing EOR technologies, together, these four methods have the potential to

enhance the average oil recovery factor to well over 50% (Doscher and Wise,

1976, Carrero et al., 2007).

2.6 The future of oil exploration in Oman

A report by the Oman Ministry of National Economics revealed that, despite

the Government’s efforts to expand the country’s range of income sources,

petroleum products remain the dominant income earner and driver of the Oman

24
economy. In 2006, oil and gas exports accounted for approximately 80% of all

export earning revenue and more than 20 international companies are now

exploring for oil and gas throughout the country. As an example, in early 2008,

a new offshore exploration contract was signed by the Oman Ministry of Oil

and Gas, which extended the Gulf of Oman offshore concession area by

23,850 km2, in addition to the 21,000km2 already allocated in Block 18 (Prabhu,

2007).

The current world oil price makes exploration of geologically challenging

reservoirs economical. The Oman Government’s pursuit of new offshore

explorations and embarking on new EOR technologies is a mark of commitment

to a sustainable oil supply (Al-Shaibany, 2007).

25
26
Chapter 3 SAMPLING AND MEASUREMENT
TECHNIQUES

3.1 Introduction

Various measurements were performed on scales, sludge and soil sediment,

both in-situ and on physical samples collected from the study locations. The in-

situ analysis consisted of: (a) collecting gamma spectra measurements using a

portable gamma spectroscopy system consisting of a Pb shielded 2 ¼” NaI(Tl)

scintillation crystal connected to a multi-channel analyser (MCA, model 7000

Rainbow) with 1024 channels; (b) gamma dose rate measurements using an

energy compensated Geiger-Müller (GM) probe Mini Instrument Type 6-80;

and (c) charcoal cups analysis, for determining radon exhalation rates. On the

other hand, the physical samples underwent: (a) gamma spectroscopy analysis

using an Ortec EG&G high purity germanium detector (HPGe); and (b)

determination of radon exhalation, using a specially designed emanometer.

Gamma dose rate measurements were carried out along with gamma

spectroscopy measurements, on both treated and untreated sludge. Onsite total

gamma counts were also collected over a preset duration of 600 s and charcoal

cups were planted to determine 222Rn exhalation at the same locations. Physical

samples were also collected from piles and strips, which were then transported

to the Medical Physics Unit Laboratory in Muscat, where they underwent

gamma spectroscopy and 222Rn activity flux analysis.

27
3.2 Dating of petroleum scale and sludge

Radionuclide activity ratios can be used to date scale and sludge samples,
228
using two different methods. The first method makes use of the Ra:226Ra

activity ratio, where the former has a shorter half life than the latter. This

method is valid, provided that the radium isotopes incorporated into a radium

insoluble mineral approximate a chemically closed system (Zielinski et al.,

2001, Al-Masri and Aba, 2005). Observations made by Al-Masri (2006) and

Zielinski et al. (2001) have shown that this ratio is fairly constant for specific

formations and varies from 0.5-2 for nascent samples, which corresponds to

Th:U mass ratio of 1.5 to 6. Ahmad et al. (2003) and Al-Masri (2006) have

illustrated a potential use of this ratio, whereby the ratio which is obtained from

produced water samples can be used to determine if two oil wells are sharing the

same reservoir. Similarly, if the ratio for a certain reservoir changes over time,

this can indicate produced water breakthrough from a nearby water source. We

did not use 228Ra:226Ra activity ratio for the purpose of reservoir fingerprinting.

The second method for dating petroleum sludge and scale samples used the
228
Th:228Ra ratio. In this method, a zero activity concentration of 228
Th is

assumed at the start of sludge formation. This is because the produced water co-
228
extracted with crude oil is thorium free and an ingrowth of Th takes place
228
with the decay of Ra, whereby the parent-progeny transient equilibrium ratio

approaches 1.5 (Figure 3.1).

28
 1.50

1.25
Relative Activity

1.00
Th-228/Ra-228 activity ratio

0.75 Ra-228 decay

Th-228 accumulation
0.50

0.25

0.00
0 5 10 15 20 25

Time (years)

Figure 3.1: The relative activity ratio of 228Th/228Ra and the relative decay of 228Ra.

The first method can be used to find the age of scale and sludge samples up
228
to 40 years, provided the initial Ra/226Ra ratio is known. Beyond this, the
228
Ra would have gone through more than seven half lives, and may no longer

be detectable enough to make accurate estimates of age. In contrast, the second

method is more suitable for estimating the age of relatively new scale or sludge,

typically less than 10 years. This is because as the change in relative activity

beyond 10 years approaches the 1.5 transient equilibrium ratio, it becomes more

difficult to resolve age with acceptable uncertainty.

29
3.3 In-situ gamma spectroscopy

A portable gamma spectroscopy system was used to collect gamma spectra

measurements in the field (Figure 3.2 (a)). The spectrometer was energy

calibrated by Amersham Cs-137 and Co-60 standard reference sources at the

Queensland University of Technology (QUT) Radiological Laboratory,

232 238 40
Brisbane, Australia. Calibration by Th, U and K radionuclides was

performed at the CSIRO Core Library, Sydney, Australia. The calibration

facility comprised of five concrete circular slabs, namely background,

potassium, uranium, thorium and mixed, each being 0.8 m thick and 2.0 m

diameter.

In order to shield the detector from adjacent cosmic radiation and gamma

rays, and ensure consistent detection geometry over the measured area of

interest (being 1.5 m2 when the system was set at a height of 1 m), a Pb casket

was designed to surround the NaI(Tl) detector (Figure 3.2 (b)). At 3.5 cm thick

and 10.75 cm deep, the shield was able to attenuate approximately 82% of

2.615 MeV (208Tl ), 84% of 1.765 MeV (214Bi) and 85% of 1.461 MeV (40K) of

incident gamma radiation. Although the 18 kg shield was not able to eliminate

the effects of incident radiation completely, a larger shield would not have been

easily portable, so a compromise had to be made between practicality and

accuracy of the gamma spectroscopy measurements. A tripod was used to

mount the portable NaI(Tl) gamma spectroscopy system, including the Pb

shield, at a height of 1 m, and the spectra were recorded for a preset duration of

600 s.

30
 (a) (b)

Figure 3.2: (a) In situ gamma spectroscopy, and (b) A lead shield (designed and
poured at QUT) for shielding the NaI(Tl) probe of the portable gamma
spectroscopy system.

The spectra were then downloaded from the MCA to a laptop and an energy

calibration was applied. Carefully determined regions of interest (ROI) were

used to obtain total counts under the three major peaks: 1.461 MeV (40K),

1.765 MeV (214Bi) and 2.615 MeV (208Tl ). The peaks had a range of 1.43-1.49,

1.69-1.87 and 2.55-2.67 MeV, respectively. An algorithm was also developed to

find factors by a 3x3 inverse matrix method, that were applied on 40K, 214Bi and
208
Tl peak counts in order to strip peak cross-talk and obtain activity

concentrations of these radionuclides in Bq kg-1.

238 232
In ambient soils, U and Th are in secular equilibrium with their
238 232
progeny, however because the U and Th series in the petroleum sludge
226 228
samples started from Ra and Ra, respectively, it was evident that the

equilibriums of the two series had been disturbed. The 238U progeny 214Po, 214Bi,
214
Pb, 218Po and 222Rn were in secular equilibrium with unsupported 226Ra, while
232 208 212 212 212 216 220 224
the Th progeny Tl, Po, Bi, Pb, Po, Rn and Ra were in

31
 228 228 228
secular equilibrium with supported Th. Further, Th and Ac were also in
228
transient and secular equilibrium with Ra, respectively. In the above two
222 220
series, Rn and Rn radioactive gases were assumed to have been fully

retained in the surveyed samples. For ambient soil, because secular equilibrium

is assumed with 232Th, the branching ratio corrected 208Tl activity concentration

would represent all of its predecessor radionuclides. However, because the

series starts from 228Ra in sludge, transient equilibrium exists between 228Th and
228 208
Ra, and thus the branching ratio corrected Tl activity concentration would
228 228
only represent predecessors up to Th. This makes determination of Ra by

the portable NaI(Tl) system for petroleum sludge complex because; (a) 228Th is

only present by ingrowth, and therefore a fresh sludge may have a significant
228 208 228
amount of Ra, but zero Tl due to zero Th, resulting in false activity

concentration for 228Ra, (b) Due to the ingrowth of 228Th into 228Ra, the ratio of
228
Th:228Ra will vary according to sample age until 228
Th reaches transient
228
equilibrium with Ra with an equilibrium factor of 1.5. This makes it

impossible to accurately determine the activity concentration of 228Ra unless the

ratio of 228Th:228Ra is known by other means.

3.4 Laboratory gamma spectroscopy

3.4.1 Sample collection and preparation

Sludge Samples: A number of 100-300 g surface sludge samples were

collected from freshly removed sludge, sludge piles, sludge strips, sludge

storage barrels, a sand waste and beads. Those samples that were exposed to

sunlight for an extended period of time were quite dry, while those that were

32
recently removed from separation tanks or stored in barrels, tended to be more

oily. Following collection, each sludge sample was placed in a standard 500 mL

sample bag. The bags were sealed, labelled with the date, time, sample type and

samplers name, and then transported to the laboratory for analysis. The oily

sludge samples were dried in the laboratory at 110 °C for 24 h. The dry samples

were then crushed, homogenised and passed through a 2 mm sieve. The samples

were then packed and pressed into petri dishes, which were sealed using

adhesive tape. Typical sample mass in the petri dish was about 0.1 kg. In some

cases, coarse non-crushable gravel with greater than 2 mm diameter was left

over. This material was monitored for radioactivity by a portable Mini

Instrument 900 series scintillation count rate meter and was found to emit

radioactivity at ambient levels, which may have resulted in an over estimation

of the radioactivity concentration of some sludge samples by up to 10%.

Scale Samples: Scales are generally chunky, hard, and in some cases brittle.

The scales collected in this study were from pipes previously used in the Fahud

oil fields of the Northern Oman Directorate. These pipes were used for pumping

produced water to injection pump stations, either for disposal or for re-injection

into reservoirs, as part of the EOR ‘water flooding’ process. They were

decommissioned because they became clogged with scales, and were

transported to Bahja NORM store yard in 1999. A spatula was used to collect

100-300 g scale samples from each pipe, penetrating the entire depth of the

scale deposited along the pipes internal wall. Following collection, each scale

sample was placed in a standard 500 mL sample bag, as per the methodology

outlined above. As the collected scale samples were already dry, solid and

33
brittle, they did not require drying. The samples were then crushed,

homogenised and packed in petri dishes, also according to the methodology

outlined above.

A further 12 samples of gas scale were also collected, however these

samples were only 50-100 g in weight, since many of the pipes they were

collected from were tightly capped, and thus we were unable to obtain samples

from many of the pipes. In addition, those pipes that were accessible only had

small amounts of gas scale that could be sampled. The gas scale samples

consisted of dry, flat flakes, about 1 mm thick and ranging from 0.01-20 cm2 in

area. These samples were then handled according to the same methodology used

for the original scale samples.

Sediment Samples: Six sediment samples, ranging from 100-300 g, were

collected from Al Noor evaporation pond, using a metal scooper. The samples

were placed in plastic bottles and transported to the laboratory in Muscat, where

they were dried at 110 °C for 24 h, before being crushed, homogenised and

passed through a 2 mm sieve. The homogenised samples were then packed and

handled according to the same methodology outlined above. In order to avoid

cross-contamination, sample preparation instruments were wipe-cleaned after

handling each individual sample.

3.4.2 Gamma spectroscopy measurement procedure

The high purity germanium (HPGe) detector system that was used to

measure the gamma spectra of the collected samples was housed in Laboratory

34
2043 at Sultan Qaboos University (SQU), Muscat. The system consisted of an

EG&G Ortec spectrometer, with a pop top semi-conductor detector (diameter:

59.0 mm, length: 74.2 mm), with 30% relative efficiency. It had a ‘full width at
57
half maximum’ (FWHM) of 0.807 keV for the 122 keV peak of Co, and
60
1.71 keV for the 1.33 MeV peak of Co. The detector was shielded against

background radiation by a 10 cm thick Pb castle.

The HPGe was energy calibrated daily, using a geometry reference source

standard in a 1000 mL marinelli beaker with known isotopes. This standard

complies with the requirements for traceability to the National Institute for

Standards and Technology (NIST), and was also used for efficiency calibration

of the system. However, because the samples used in this research were placed

in petri dishes for analysis, a separate geometry correction calibration was

carried out on the HPGe, using known volumes and activities of standard

radionuclides, in order to accommodate for the petri dish geometry. Background

spectra were also recorded and corrected during sample spectrum analysis.

The main radioisotopes identified by this study in petroleum NORM are

40 227
radium isotopes and their progeny, along with K and Ac. Because of the
226 235
Ra strong overlap with the U 185.7 keV peak (actinium series - emission

intensity 57.5%), many gamma spectrometers do not rely on the main

186.1 keV peak of 226Ra (uranium series - emission intensity 3.5%) to determine
226
its activity concentration. Therefore, gamma emitting Ra progeny (214Pb,
214 226
T½: 26.8 minutes and Bi, T½: 19.9 minutes) are used to obtain Ra activity
222
concentration. However, due to the presence of the gaseous intermediate Rn

35
 238
(refer to U decay series in Chapter 1, Figure 1.2 (a)) the samples had to be
222
sealed for 21 days, in order to allow the Rn and its progeny to reach
226
equilibrium with their parent radionuclide. The Ra activity could then be

obtained by calculating the error weighted average of gamma emitting 214Pb and
214 238 232
Bi. Assuming similar activity concentrations of U and Th, and a 1:20
235 238 235 226
ratio between U and U, the contribution of U in the Ra peak was

found to be 2.7%. Due to the HPGe’s 30% relative efficiency, along with its

energy efficiency peak at 160 keV, the system was found to have a low
210
efficiency for radionuclides with low gamma energy, such as Pb (46.5 keV).
210
However, samples with a large activity concentration of Pb were an

exception, as was the case with the oil and gas scale samples collected during
210 228 40
this research. Activity concentrations of Pb, Th and K were also

determined directly from their respective gamma lines. However, activity

concentrations of radioisotopes with a weak or no gamma signal (for example;

227 228
Ac and Ra) were determined by their progeny (227Th and 228
Ac) gamma

lines, respectively.

The gamma spectrum for each sample was obtained over a 17 hour

timeframe. SQU’s HPGe system utilises Gamma Vision 5.1 software for

spectrum analysis. This software adjusts for the effects of interfering peaks,

should the presence of a second radionuclide be confirmed. As such, the

235
Gamma Vision software was able to adjust for the contribution of U to the
226
observed 186 keV peak, thus allowing for the Ra activity concentration to be

determined immediately. However, because SQU’s HPGe system was also used

for the University’s own work, the analysis of field samples was sometimes

36
delayed for up to three months. Even though 228Th has a relatively short half life
228
of 1.9 years, it is in transient equilibrium with Ra (T½: 5.75 years); and since

radioactivity is transported by produced water and 228Th is not water soluble, an

initial activity concentration of zero was assumed at the time of sludge/scale

formation. However, all reported gamma spectroscopy data were still needed to

be corrected for 228Ra and 228Th decay. To correct for 228Ra decay it is a straight
228
forward exponential relationship, however for the Th decay correction, the
228
age of the sample had to be calculated based on an analysis of the Ra/228Th
228
activity ratio at the time of collection. Thus, using the Ra activity
228
concentration at the collection date, Th activity concentration was calculated

for each sample (see Section 3.2).

3.5 Comparison between in-situ and laboratory gamma

spectroscopy measurements

Overall, 24 sampling locations were analysed for gamma spectra, using both

in-situ and laboratory gamma spectroscopy. The corresponding results for each

location were then compared and checked for correlation. The main

radionuclides that were compared are illustrated in Figures 3.3 (a-d). From these
226 228
figures it can be seen that the field and laboratory Ra, Th and 40K activity

concentrations compared well, giving linear fit and correlation coefficients as

follows:

ARa-226 Field = (1.05 ± 0.05) ARa-226 Lab (R2 = 0.96), (3.1)

2
ATh-228 Field = (1.09 ± 0.05) ATh-228 Lab (R = 0.96), and (3.2)
2
AK-40 Field = (1.10 ± 0.12) AK-40 Lab (R = 0.78) (3.3)

37
 228 228
However, the linear fit of the field Th to laboratory Ra activity

concentration comparison was significantly further away from 1:

ATh-228 Field = (1.57 ± 0.11) ARa-228 Lab (R2 = 0.91) (3.4)

This difference is because, due to the absence of the primordial series parent
232 228
Th in the oil industry NORM, Th reaches transient (and not secular)
228
equilibrium with Ra – hence the ratio approaches 1.5, instead of 1. This fact

was considered while applying in-situ gamma spectroscopy techniques for

NORM measurements.

38
 (a) AField = (1.05 ± 0.05) ALab (b) AField = (1.09 ± 0.05) ALab
R2 = 0.96, n = 24 R2 = 0.96, n = 23
6
1800
Field NaI - 226Ra (kBq kg-1)

5 1500

Field NaI - 228Th (Bq kg-1)

4 1200

3 900

2 600

1 300

0 0
0 1 2 3 4 5 0 300 600 900 1200 1500

226 -1 228
Lab. HPGe - Ra (kBq kg ) Lab. HPGe Th (Bq kg-1)

(c) AField = (1.10 ± 0.12) ALab (d)

AField = (1.57 ± 0.11) ALab
R2 = 0.78, n = 24 R2 = 0.91, n = 20
1,050 600
Field NaI - 228Th (Bq kg-1)
Field NaI - 40K (Bq kg-1)

875 500

700 400

525 300

350 200

175 100

0 0
0 150 300 450 600 750 0 70 140 210 280 350

Lab. HPGe 40K (Bq kg-1) Lab. HPGe 228Ra (Bq kg-1)

Figure 3.3: Correlation between field portable NaI(Tl) and laboratory HPGe activity
concentration readings for: (a) 226Ra Field vs 226Ra Lab, (b) 228Th Field vs 228Th Lab, (c) 40K Field
vs 40K Lab and (d) 228Th Field vs 228Ra Lab .

39
3.6 In-situ gamma dose-rate measurements

The Mini-Instrument 6-80 dose rate meter was used to assess gamma

radiation dose rate above piles and strips, located at the Bahja, Nimr and

Marmul sludge farms. The meter consisted of an electrometer, connected to an

energy compensated Geiger-Müller (GM) tube, which was mounted on a tripod

at a height of 1 m above ground. The electrometer provided two separate

readings, an instantaneous absorbed dose rate in air (in µGy h-1) on an analogue

scale, and pre-set time total counts at 600 s, on a digital display. The count rates

(s-1) were divided by a calibration factor of 17.1 to obtain the effective dose rate

in µSv h-1. This factor was obtained through calibrating the system against an

Amersham certified standard (Cs-137 – source number 3702GF) and the

measured dose rates were then verified, by calculating the external exposure

rates using (UNSCEAR, 2000) dose coefficients.

226 228
The Ra, Ra and 40K activity concentrations (in Bq kg-1) obtained from

both in-situ and laboratory gamma spectroscopy measurements were also used

to calculate the dose rate in air D (in µGy h-1) at a 1 m height from the ground,

according to the following equation:

D = (0.462 A[238U] + 0.604 A[232Th] + 0.0417 A[40K])/1000 (3.5)

where A[238U], A[232Th] and A[40K] are the activity concentrations (in Bq kg-1)

for 226Ra, 228Ra and 40K, respectively.

40
3.7 Radon activity flux measurements using charcoal
cups

Activated charcoal is known to adsorb radon gas onto its surface. Brass

charcoal canisters, or cups, containing 25 g of fine activated charcoal (secured

by a wire spring over metal mesh) were used to collect passive field readings of
222
Rn exhalation from the sludge piles. These cylindrical cups were open at one

end, with a height and base area of 0.080 m and 0.0029 m2, respectively. Prior

to use, the charcoal cups are annealed for 8-10 h, at a temperature of 110 ºC.

The cups were then allowed to cool for 20 min, before being covered by a

polyethylene lid and sealed with adhesive tape.

Before field measurements were conducted, a ‘standard’ cup was prepared

using a 25 g sludge sample, with 226Ra and 228Ra activity concentrations of 4030

± 21 and 343 ± 7 Bq kg-1, respectively. An epoxy resin was then poured over the

seal, in order to ensure that the 222Rn would not escape. When the 222Rn reached
226
secular equilibrium with its parent Ra three weeks later, the standard was

ready for use.

In the field, the polyethylene lids were removed from the annealed cups and

they were planted upside down on the sludge piles, with the rim of the cup

buried approximately 1 cm into the ground (Figure 3.4). Two cups were planted

for each location, where the mean value was then used. The cups were left in the

field for four days, before being removed and immediately sealed. They were
222
then allowed to sit for a minimum of four hours, so that the Rn could reach

equilibrium with its short lived gamma emitting progeny 214Pb and 214Bi.

41
Figure 3.4: Charcoal cups planted on a sludge pile.

A 600 s gamma spectrum was then collected from the cups using the

NaI(Tl) detector. Planting, removal and counting dates and times were noted, in

order to calculate exposure (te), delay (td) and counting (tc) time intervals. The

net count rate was obtained from the spectra region of interest (ROI) covering
222
the gamma peak energies of Rn progeny (Pb-214 peaks at 242, 295 and

352 keV and Bi-214 peak at 609 keV). The set range was from 223-725 keV,

corresponding to channels 60-195 on the MCA. Rn-222 exhalation rate in the

charcoal cup was then interpolated from its gamma emitting progeny 214Pb (T½:
214
26.8 min) and Bi (T½: 19.9 min) using the following equation (Spehr and

Johnston, 1983):

R ⋅ λ 2 ⋅ t c ⋅ e λt d
J= (3.6)
ε ⋅ a ⋅ (1 − e −λtc ) ⋅ (1 − e −λte )

where te, td and tc are the exposure time in the field, the delay time between

retrieval from the field and counting in the laboratory, and the counting time (s);

J is the average 222Rn exhalation rate (Bq m-2 s-1) over the exposure time te; R is

the net count rate (s-1) post background subtraction obtained during tc; λ is the

42
decay constant (s-1) for 222
Rn; a is the surface area covered by the charcoal

canister (m2); and ε is the counting efficiency of the detector system (s-1 Bq-1).

3.8 Radon exhalation rate measurements using the

emanometer

The emanometer was calibrated using certified Pylon radon gas (Model RN-

1025). Figure 3.5 (a) shows a schematic diagram of the emanometer, which was

housed in a secure wooden box with all of its components secured in

predetermined slots, as shown in Figure 3.5 (b). Due to time constraints during

the field visits, only a limited number of charcoal cup applications could be
222
performed. Therefore, laboratory assessment of Rn exhalation rates was also

undertaken for twenty corresponding field samples. These measurements were

then cross-referenced with the charcoal cup measurements, in order to verify the

accuracy of the emanometer. All of the reported radon exhalation rates (apart

from two out of the four Oman ambient soil samples) in Chapter 6 are from

values obtained using the emanometer.

43
 (a)
Emanometer assembly schematic

Electronics

8 mm tube

Flow rate meter

Pump inflow
Valves

w
tflo
ou
Sample
chamber

PM-tube Sample

Absolute filter
(Cotton wool) Table
Signal and power lines ZnS(Ag)
scintillation
chamber

(b)

Figure 3.5: (a) Schematic diagram of the emanometer, and (b) The emanometer in
its wooden box housing.

222
This technique for the determination of Rn exhalation rate made use of

ZnS(Ag) scintillation chambers, coupled with photo-multiplier tubes. The main

components of the emanometer were: 2 x ZnS(Ag) scintillation chambers,

44
2 x photo-multiplier tubes coupled to the scintillation chambers, 2 x DayBreak

digital power supplies and counters, 2 x pumps with flow-rate meters, 2 x cotton

wool absolute filters and a suite of sample chambers. Each sample chamber was

a 3.5 L PVC cylinder with a clear Perspex lid (Figure 3.6 (a)). The cover was

fitted with inlet and outlet valves, and an O-ring, along with six screws and

butterfly nuts were fastened to the cover, in order to obtain an air tight seal

between the chamber and the lid. An 8 mm capillary tube connected the sample

chamber to the rest of the system.

(a) (b)

Figure 3.6: (a) Emanometer’s airtight PVC sample chambers with FESTO valves
and Perspex cover, and (b) a sludge sample wrapped in perforated textile
material, labelled and ready for 222Rn counting.

Sample collection has been described in Section 3.4.1. The samples are kept

as intact as practically possible in order to obtain the same 222Rn exhalation rate

found in the field. The samples analysed by the emanometer included petroleum

scales, treated and untreated sludge from sludge farms, sludge stored in barrels,

sediment soil from a produced water evaporation pond and ambient soil. Each

0.25 kg sample was wrapped in 225 cm2 of perforated textile, tied with a wire

ribbon, labelled and placed on a plastic table inside the sample chamber
222
(Figure 3.6 (b)). The chamber was then sealed for 24 h to allow for Rn gas

45
accumulation, before being connected to the system. Air was then pumped

through a closed loop, at a rate of 6 L min-1, moving from the sample chamber,

through a wool cotton absolute filter, into the ZnS(Ag) scintillation chamber,

through the pump and the flow rate meter, then back to the sample chamber.

46
Chapter 4 RADIOACTIVITY CONCENTRATION
OF SCALE, SLUDGE AND SOIL
SEDIMENT, FROM THE OIL FIELDS
OF THE SOUTHERN OMAN
DIRECTORATE

4.1 Introduction
The presence of technologically enhanced NORMs in petroleum industry

scales and sludge has been reported by many of the world’s oil producing

countries. In this work, we have attempted to characterise and quantify this

radiation, based on samples taken from the oil fields of the Southern Oman

Directorate (SOD). This chapter will report the radioactivity concentrations of

sludge, oil and gas scales, and evaporation pond soil sediment, as well as the use

of radioisotopes to date scales and sludge.

Gamma spectroscopy measurements were performed on various solid waste

samples, including: (1) nascent sludge and sludge in Bahja, Nimr and Marmul

sludge farms; (2) oil and gas scales, and sludge stored in barrels in Bahja

NORM store yard; and (3) sediment in Al-Noor evaporation pond. Sludge

samples were also tracked from its initial point of accumulation at the separator

tanks, to its final destination at the sludge farm or in barrels at the NORM store

yard.

47
4.2 Radioactivity in sludge
Oman generates approximately 7.2 x 104 tonnes of sludge per annum (Al-

Futaisi et al., 2007). As mentioned in Chapter 1, Section 1.3, the word ‘sludge’

refers to a mixture of hydrocarbon, mud, natural radionuclides, sediments,

bacterial growth, corrosion particles and some scale debris. In Oman, the

presence of petroleum industry NORMs was first discovered in a sludge sample

removed by a pig device from the Hasirah of Zauliyah line, in the Bahja cluster

in 1997. Today, PDO conduct an analysis of all sludge removed from its storage

and separator tanks, using a Mini-Instrument 900 series count rate meter, with a

gamma scintillation probe (Model 44A). The nominal background surface count

rate for these meters is 3 CPS and sludge samples with count rates 5 CPS higher

than the nominal background (i.e. 8 CPS) are considered to be NORM

contaminated. According to an unpublished paper, presented at the ‘PDO

Workshop on NORM’ in Muscat (2005), PDO’s total accumulated sludge was

more than 3.3 x 105 tonnes and out of this mass, almost 2.0 x 104 tonnes was

NORM contaminated.

In a national ambient soil radioactivity survey carried out by Goddard

(2002), the average activity concentrations of 226Ra and 232Th in the upper 1 cm

of exposed surface soil or rock were reported as 29.7 ± 8.9 and

15.9 ± 7.6 Bq kg-1, respectively. Assuming equilibrium between 232

Th and
228
Ra, the latter reported average could be considered the national average for
228
Ra activity concentration. A report on 226Ra and 224Ra activity concentrations

in 50 oily sludge samples collected from the northern Oman oilfields was also

published by Salih et al. (2005). The activity concentrations obtained using

48
laboratory HPGe gamma spectroscopy ranged from 0.15-1 kBq kg-1 for 226
Ra,

and 0.1-0.6 kBq kg-1 for 224Ra.

4.2.1 Sludge farming

226 210
The presence of long lived radioisotopes (e.g. Ra, T½: 1602 years; Pb,
228
T½: 22.26 years and Ra, T½: 5.75 years) in sludge, at levels higher than those

found in ambient soil, poses a significant radiological hazard to the

environment. Shailubhai (1986) discussed various options for the disposal of

oily sludge, including ocean disposal, incineration and land farming. However,

the presence of toxic chemicals in the oily sludge means that ocean disposal is

not a desirable option, since aquatic organisms may be poisoned by these toxins.

Since global warming has become an issue, incineration is no longer desirable

either, because it is not only energy intensive, but it also contributes

significantly to air pollution. Land farming, on the other hand, is highly cost

effective, provided that the sludge does not contaminate clean soil and seep into

underground water supplies. Many other studies have also investigated options

for sludge farming; however none of them have addressed the issue of

radioactivity (Arora et al., 1982, Couillard et al., 1991, Prado-Jatar et al., 1993,

Brown et al., 1998, Vasudevan and Rajaram, 2001, Mater et al., 2006).

In Oman, oily sludge is currently being disposed of at sludge farms, which

utilise micro-organisms to biodegrade the complex hydrocarbons found in oil,

into naturally occurring by-products, such as carbon dioxide and water. This

process requires minimal machinery and labour inputs, and since it is able to

49
occur above ground, in areas exposed to high levels of solar radiation, it is the

most cost effective method of sludge disposal, particularly in the remote desert

oil fields of Oman.

At the time of the field studies conducted during this research, the total land

area of Bahja, Nimr and Marmul sludge farms was about 30 hectares. These

farms usually consisted of two areas – one where the excavated sludge was

heaped, and the other, a flat plot of machine compacted land dedicated for

spreading the sludge. The sludge was spread in rows, otherwise known as

‘strips’, measuring approximately 6 m in width, 75 m in length and 0.4 m in

height, and were separated by 4-8 m of open space, to allow passage for the

water tanker and other service vehicles. Table 4.1 shows the GPS locations,

estimated volume of material in untreated sludge piles and number of treated

sludge strips at Bahja, Nimr and Marmul sludge farms, at the time of our final

visit to Oman (21 April - 8 May 2007). The total volume of sludge found in the

three farms was estimated to be around 34,000 m3.

Table 4.1: Bahja, Nimr and Marmul sludge farm locations, estimated volume of
untreated sludge in piles and number of treated sludge Strips at the time of this
study (Jan 2006 – June 2007)
Sludge farm Geographical location Sludge pile Number
Latitude Longitude volume (m3) of Strips

Bahja N 19° 52.8’ E 56° 02.0’ 10,000 42

Nimr N 18° 33.3’ E 55° 51.9’ 17,000 147

Marmul N 18° 12.6’ E 55° 17.5’ 7,000 64

Total 34,000 253

50
 After the sludge is delivered to the sludge farms, the heaps are transported to

the strip site, where the sludge is spread, before being mixed with clean soil by

an earth moving machine (skid loader). Alternatively, sludge can be mixed with

clean sand before it is transported to the strip site. The strips are then tilled and

watered on daily basis, in order to maintain optimal aeration and moisture

conditions for the biodegradation and evaporation of volatile compounds

(Figure 4.1 (a-f)). Typically, the soil to sludge ratio ranges from 1-5:1,
226
depending on the Ra activity concentration of the sludge. Along with daily

tilling, this not only serves to assist bioremediation, but it also helps to dilute the

radioactivity present in the sludge.

A total of 55 untreated sludge samples were analysed from the three sludge

farms - 25 from Bahja, 14 from Nimr and 16 from Marmul. A further 57 treated

sludge samples were also analysed - 12 from Bahja, 16 from Nimr and 29 from

Marmul (see Chapter 3, Sections 3.2.1 and 3.2.2 for details on sampling and

measurement procedures).

51
 a b

c d

e f

Figure 4.1: The sludge farming process: (a) sludge removed from a separation
tank, (b) untreated sludge piles, (c) sludge piles after transport to the farming
area, (d) a typical sludge strip, (e) watering the sludge strips, and (f) tilling the
sludge strips.

52
4.2.2 Radioactivity in ambient soil

The radioactivity of ambient soil samples from Bahja, Al-Noor, Nimr and
226
Marmul are shown in Table 4.2. The mean activity concentrations of Ra,
228
Ra, 228Th and 40K were 34.2 ± 3.8, 8.1 ± 1.3, 7.1 ± 0.8 and 151 ± 55 Bq kg-1,

respectively. Bahja 40K activity concentration (293 ± 8 Bq kg-1) was three times

higher than the mean activity concentration for the other three sites

(104 ± 6 Bq kg-1). As expected, the mean 228

Th:228Ra activity ratio for the four
228 228
sites was close to one (0.89 ± 0.09), since Th and Ra were likely to be in

secular equilibrium with 232Th.

A detailed study of Oman’s ambient terrestrial radioactivity concentrations

was performed by Goddard (2002). The study reported mean activity

concentrations for 15 samples from the Wusta region (the same region where

this research was conducted), being 36.2 ± 8.2, 16.4 ± 5.5 and 166 ± 27 Bq kg-1
226 232 40
for Ra, Th and K, respectively. Taking into account the uncertainties of

these types of measurements, the ambient soil concentrations found in this

research are similar to those found by Goddard in 2002. However, a study

conducted by the United Nations (UNSCEAR, 2000) reported population

weighted natural radionuclide activity concentrations in soils to be 35, 30 and

400 Bq kg-1 for 238

U, 232
Th and 40
K, respectively. In comparison to these
232 40
findings, the desert environment of Oman seems to have lower Th and K

concentrations than those found elsewhere in the world.

53
Table 4.2: Activity concentration (Bq kg-1) for ambient soils of Bahja, Al-Noor, Nimr and Marmul and the world average (UNSCEAR,
2000) (uncertainties represent counting error)
226 228 228 40 137 228
Sample ID Geographical location Ra Ra Th K Cs Ra:226Ra 228
Th:228Ra
Latitude Longitude
Bahja N 19° 53.047' E 56° 01.753' 38.1 ± 5.4 11.3 ± 1.4 9.1 ± 1.4 293 ± 8 1.02 ± 0.23 0.30 ± 0.08 0.81 ± 0.22

Al Noor N 18° 41.391' E 55° 30.376' 30.4 ± 5.2 7.7 ± 0.8 7.1 ± 0.4 108 ± 5 0.58 ± 0.18 0.25 ± 0.07 0.92 ± 0.15

Nimr N 18° 33.257' E 55° 51.864' 27.2 ± 1.3 5.7 ± 0.4 5.7 ± 0.4 111 ± 2 < 0.12 0.21 ± 0.03 1.00 ± 0.14

Marmul N 18° 12.562' E 55° 17.337' 41.2 ± 4.9 7.8 ± 1.1 6.5 ± 1.5 93 ± 5 < 0.44 0.19 ± 0.05 0.83 ± 0.31

Mean ± SE 34.2 ± 3.8 8.1 ± 1.3 7.1 ± 0.8 151 ± 55 0.24 (0.03) 0.89 (0.05)
-
Standard 6.5 2.3 1.5 95 0.05 0.09
Deviation
-
# #
World 35 30 30 400
Median
#
Assuming secular equilibrium of 228Ra and 228Th with 232Th

54
4.2.3 Radioactivity in the sludge recovered from a separator

tank

PDO cleans its separator tanks approximately every 5 years, depending on

the sludge accumulation rate at the bottom of the tank. After cleaning, NORM

contaminated sludge samples are sent to Sultan Qaboos University (SQU) for
226
gamma spectroscopy analysis, in order to determine Ra activity

concentration, and thus, the fate of the sludge. NORM contaminated sludge,
226
with a Ra activity concentration equal to or higher than 1 kBq kg-1, is

transported to the Bahja NORM store yard for storage. NORM contaminated
226
sludge with a Ra activity concentration less than 1 kBq kg-1 is sent to the

Bahja, Nimr and Marmul sludge farms.

Six sludge samples were collected from a newly cleaned separator tank at
226 228 228 40
Nimr sludge farm. They were assessed for Ra, Ra, Th and K
228
radioactivity and Ra:226Ra and 228
Th:228Ra ratios (refer to Chapter 3, Section

3.2.1 and 3.2.2 for details on sampling and measurement procedures), in order

to determine the initial radioactivity and the age of the sludge sediment. From
226 228 228 40
Table 4.3 it can be seen that the mean Ra, Ra, Th and K activity

concentrations were 588 ± 106, 264 ± 53, 296 ± 52 and 109 ± 20 Bq kg-1,
40
respectively. While the mean K activity concentration was similar to the
226 228 228
ambient soil value for Nimr sludge farm, the Ra, Ra and Th activity

concentrations were significantly higher than the Nimr ambient soil

concentrations.

55
Table 4.3: Activity concentration (Bq kg-1) and individual reading error of freshly removed sludge from a Nimr station separator tank
Sample ID 226
Ra 228
Ra 228
Th 40
K 228
Ra:226Ra 228
Th:228Ra 228
Ra:226Ra Age of sludge
ratio at deposition (years)
0.96 5.7
NFS 1 446 ± 17 206 ± 4 221 ± 5 149 ± 8 0.46 ± 0.03 1.08 ± 0.04 0.86 0.77 5.2 4.8
0.97 6.6
NFS 2 391 ± 15 163 ± 3 186 ± 4 89 ± 7 0.42 ± 0.02 1.15 ± 0.05 0.85 0.76 6.0 5.5
0.96 6.1
NFS 3 985 ± 24 446 ± 5 496 ± 7 119 ± 12 0.45 ± 0.02 1.13 ± 0.03 0.89 0.83 5.8 5.5
0.93 4.8
NFS 4 697 ± 24 352 ± 5 346 ± 6 117 ± 13 0.51 ± 0.02 0.99 ± 0.03 0.86 0.79 4.5 4.2
7.4
NFS 5 363 ± 12 139 ± 3 207 ± 5 32 ± 6 0.38 ± 0.02 1.49 ± 0.07 7.0a 6.6
1.00 6.7
NFS 6 648 ± 19 280 ± 5 321 ± 6 151 ± 10 0.43 ± 0.02 1.16 ± 0.04 0.89 0.80 6.2 5.7

Maximum 985 446 496 151 0.51 1.49

Minimum 363 139 186 32 0.38 0.99
Median 547 243 271 118 0.44 1.14
Standard Deviation 238 118 117 44 0.04 0.17
0.97 6.3
Mean ± SE 588 ± 106 264 ± 53 296 ± 52 109 ± 20 0.44 ± 0.02 1.16 ± 0.08 0.87 0.79 5.8 5.4

Nimr Ambient Soilb 27.2 ± 1.3 5.7 ± 0.4 5.7 ± 0.4 111 ± 2 0.21 ± 0.03 1.00 ± 0.14
a
Based on 228Ra:226Ra activity concentration ratio. Not included in the average
b
From Table 4.2

56
 From Table 4.3 it can also be seen that the average 228Th:228Ra activity ratio

was 1.16 ± 0.17, indicating that the sludge was approximately 5.8 56..43 years old,

which is consistent with the company’s separator tank cleaning interval of

5 years. The age of individual samples was then used to determine the
228
Ra:226Ra ratio at the time of deposition. Since 226
Ra (T½: 1602 years) decay

would be insignificant in 5.8 years, no decay correction was necessary when

228
calculating the mean Ra:226Ra activity ratio at the time of deposition, which

was found to be 0.87 00..97

79 . In addition, the deposition activity ratio corresponded

232
to a Th:238U mass ratio of 2.6. These values were similar to those found by
228
Al-Masri and Aba (2005), who reported a mean Ra:226Ra activity ratio and
232
Th:238U mass ratio of 0.76 and 2.3, respectively.

As outlined in Chapter 3, Section 3.2, the initial formation of sludge is

usually free of 228Th. Build up, and ingrowth of 228Th (T½: 1.9 years) takes place
228
as Ra (T½: 5.75 years) decays, until a transient equilibrium is reached. In
228
contrast, considering the difference in the half lives, Ra activity reduces

rapidly relative to 226Ra, which explains the inverse trend that was demonstrated

by the 228Ra:226Ra and 228Th:228Ra activity ratios (Figure 4.2).

57
 0.6

Ra:226Ra activity ratio

0.5

0.4
228

0.3
0.8 1.0 1.2 1.4 1.6

228
Th:228Ra activity ratio

Figure 4.2: Relation between 228Ra:226Ra and 228Th:228Ra activity ratios.

4.2.4 Radioactivity in untreated piles at sludge farms

A summary of the activity concentrations found in untreated sludge from the

Bahja, Nimr and Marmul sludge farms, is presented in Table 4.4, while the

individual values are displayed in Tables 4.5, 4.6 and 4.7.

Bahja Sludge Farm: A preliminary survey of the untreated sludge piles,

using a portable gamma count rate meter, revealed that about 75% of the total

piles had gamma counts close to ambient soil, and therefore no samples were

collected from those piles. The remaining 25% had enhanced activity

concentrations equal to or greater than the set limit of 1 kBq kg-1 (Petroleum

Development Oman, 2005), which meant that they were not suitable to be used

in the sludge farming process . These high activity sludge piles were segregated

58
from the rest of the piles, in an area measuring approximately 600 m2 and they

will remain there until an alternative disposal or treatment method is approved.

226 228 228
The mean (± standard error) Ra, Ra, Th and 40K activity concentrations

for these high activity piles were found to be 3289 ± 264, 261 ± 19, 338 ± 26

and 427 ± 50 Bq kg-1, respectively. The mean 228

Th:228Ra and 228
Ra:226Ra

activity ratios were then used to estimate the age of the sludge, which was found

to be 9.0 ± 0.4 and 15 years (assuming the initial 228Ra:226Ra ratio is the same as

Nimr nascent sludge), respectively. As expected, these age estimates for Bahja

farmed sludge were 3-9 years more than the age of sludge freshly removed from

the tank, as determined in Section 4.2.3.

226
Nimr Sludge Farm: All of the untreated sludge samples had Ra activity

concentrations less than 1 kBq kg-1 and the distribution was also less dispersed
226 228 228 40
between piles. Averages for Ra, Ra, Th and K activity concentrations

were 343 ± 35, 129 ± 13, 123 ± 14 and 433 ± 27 Bq kg-1, respectively.

Marmul Sludge Farm: On the basis of a gamma dose rate survey of the

Marmul untreated sludge piles, about 10% were expected to have activity

concentrations exceeding 1 kBq kg-1, and sample collection was biased towards

the higher activity piles. The maximum activity concentrations detected in

Marmul sludge were 3690 ± 60, 6036 ± 20, 5164 ± 20 and 720 ± 13 Bq kg-1 for
226 228 228
Ra, Ra, Th and 40K, respectively. When weighted according to the area

of higher and lower concentration piles, the mean (± standard error) activity
226 228 228 40
concentrations for Ra, Ra, Th and K were 326 ± 153, 394 ± 205, 342

± 179 and 360 ± 79 Bq kg-1, respectively.

59
Table 4.4: Sludge activity concentrations (Bq kg-1) and radioisotope ratios from Bahja, Nimr and Marmul untreated sludge piles
226 228 228 40 228
Location Ra Ra Th K Ra:226Ra 228
Th:228Ra
Bahja Median 3164 268 344 272 0.083 1.29
Mean 3289 261 338 427 0.082 1.29
Standard Error 264 19 26 50 0.004 0.01
Standard Deviation 1295 93 125 243 0.015 0.05
Number of Samples 25
Nimr Median 323 123 113 448 0.37 0.95
Mean 343 129 123 433 0.40 0.95
Standard Error 35 13 14 27 0.03 0.02
Standard Deviation 128 46 51 99 0.11 0.07
Number of Samples 14
Marmul * Mean 356 394 342 360 0.60 0.85
* Standard Error 153 205 179 79 0.12 0.04
* Standard Deviation 342 421 428 247 0.29 0.10
Number of Samples 16
* Area weighted values due to distinct low and high radioactivity sections

60
Table 4.5: Activity concentrations (Bq kg-1) of untreated Bahja sludge piles
226 228 228 40 228
Sample ID Location 40Q UTM Ra Ra Th K Ra:226Ra 228
Th:228Ra
Easting Northing
BHJP 1 * 398306 2198873 2210 ± 40 191 ± 7 240 ± 10 185 ± 21 0.086 ± 0.004 1.26 ± 0.10
BHJP 2 * 398318 2198877 1310 ± 20 103 ± 5 132 ± 7 252 ± 15 0.079 ± 0.005 1.28 ± 0.13
BHJP 3 * 398316 2198885 2980 ± 30 203 ± 6 255 ± 9 229 ± 18 0.068 ± 0.003 1.25 ± 0.09
BHJP 4 * 398318 2198888 2150 ± 70 143 ± 11 180 ± 19 264 ± 27 0.066 ± 0.007 1.26 ± 0.23
BHJP 5 * 398318 2198898 2240 ± 40 150 ± 5 190 ± 11 254 ± 21 0.067 ± 0.003 1.27 ± 0.11
BHJP 6 * 398328 2198909 4520 ± 50 200 ± 10 376 ± 15 209 ± 23 0.066 ± 0.003 1.25 ± 0.09
BHJP 7 * 398363 2198960 4000 ± 40 253 ± 9 330 ± 16 217 ± 23 0.063 ± 0.003 1.32 ± 0.11
BHJP 8 * 5670 ± 50 373 ± 9 501 ± 13 182 ± 22 0.066 ± 0.002 1.34 ± 0.06
BHJP 9 * 5180 ± 40 345 ± 7 454 ± 3 187 ± 12 0.067 ± 0.002 1.32 ± 0.04
BHJP 10 * 5300 ± 40 345 ± 7 506 ± 6 200 ± 19 0.065 ± 0.002 1.47 ± 0.05
BHJP 11 * 1090 ± 20 92 ± 4 112 ± 5 232 ± 12 0.088 ± 0.005 1.22 ± 0.10
BHJP 12 * 4580 ± 50 309 ± 8 392 ± 12 192 ± 22 0.065 ± 0.002 1.27 ± 0.07
BHJP 13 * 3164 ± 56 253 ± 11 306 ± 20 272 ± 31 0.084 ± 0.005 1.22 ± 0.14
BHJP 14 # 398367 2198958 1955 ± 56 172 ± 14 221 ± 18 524 ± 122 0.088 ± 0.010 -

61
Table 4.5 (Continued): Activity concentrations (Bq kg-1) of untreated Bahja sludge piles
226 228 228 40 228
Sample ID Location 40Q UTM Ra Ra Th K Ra:226Ra 228
Th:228Ra
Easting Northing
BHJP 15 # 398360 2198953 2981 ± 69 289 ± 18 372 ± 24 597 ± 150 0.097 ± 0.008 -
BHJP 16 # 398355 2198950 3221 ± 71 271 ± 18 349 ± 23 566 ± 153 0.084 ± 0.007 -
BHJP 17 # 398351 2198944 3799 ± 77 315 ± 19 405 ± 25 591 ± 165 0.083 ± 0.007 -
BHJP 18 # 398342 2198933 3875 ± 79 375 ± 21 484 ± 27 779 ± 171 0.097 ± 0.007 -
BHJP 19 # 398340 2198929 4336 ± 82 366 ± 21 470 ± 26 767 ± 178 0.084 ± 0.006 -
BHJP 20 # 398333 2198920 4934 ± 89 472 ± 23 607 ± 30 758 ± 190 0.096 ± 0.006 -
BHJP 21 # 398330 2198915 2908 ± 68 258 ± 17 332 ± 22 638 ± 147 0.089 ± 0.008 -
BHJP 22 # 398320 2198906 3445 ± 73 287 ± 18 369 ± 23 954 ± 162 0.083 ± 0.007 -
BHJP 23 # 398310 2198896 2444 ± 63 268 ± 18 344 ± 23 742 ± 140 0.109 ± 0.010 -
BHJP 24 # 398309 2198890 2274 ± 60 200 ± 15 257 ± 20 409 ± 129 0.088 ± 0.009 -
BHJP 25 # 398300 2198878 1651 ± 53 198 ± 15 255 ± 19 469 ± 115 0.120 ± 0.013 -
Maximum 5670 470 607 954 0.120 1.47
Minimum 1090 92 112 182 0.063 1.22
Number of Samples 25
* Analysis by HPGe gamma spectroscopy system
#
Analysis by NaI portable gamma spectroscopy system – 228Ra value were determined by using 228Th:228Ra ratio of 1.29

62
Table 4.6: Activity concentrations (Bq kg-1) of untreated Nimr sludge piles (analysed using the HPGe gamma spectroscopy system)
226 228 228 40 228
Sample ID Location 40QUTM Ra Ra Th K Ra:226Ra 228
Th:228Ra
Easting Northing
NMRP 1 383329 2051550 531 ± 13 139 ± 3 151 ± 4 446 ± 10 0.26 ± 0.01 1.08 ± 0.06
NMRP 2 383337 2051562 403 ± 17 138 ± 5 130 ± 5 487 ± 14 0.34 ± 0.03 0.94 ± 0.07
NMRP 3 383356 2051569 291 ± 14 118 ± 3 106 ± 4 405 ± 10 0.41 ± 0.03 0.90 ± 0.06
NMRP 4 383353 2051598 314 ± 10 114 ± 3 109 ± 3 457 ± 9 0.36 ± 0.02 0.96 ± 0.05
NMRP 5 383309 2051584 320 ± 11 123 ± 2 115 ± 3 457 ± 9 0.38 ± 0.02 0.94 ± 0.04
NMRP 6 383296 2051560 285 ± 10 95 ± 3 94 ± 3 439 ± 9 0.33 ± 0.02 0.99 ± 0.07
NMRP 7 383347 2051609 639 ± 17 270 ± 4 281 ± 5 134 ± 10 0.42 ± 0.02 1.04 ± 0.04
NMRP 8 73 ± 7 55 ± 2 48 ± 2 595 ± 10 0.75 ± 0.10 0.87 ± 0.08
NMRP 9 309 ± 19 130 ± 4 119 ± 6 392 ± 14 0.42 ± 0.04 0.91 ± 0.07
NMRP 10 284 ± 14 141 ± 4 109 ± 5 451 ± 14 0.50 ± 0.04 0.77 ± 0.06
NMRP 11 361 ± 17 136 ± 5 125 ± 6 469 ± 16 0.38 ± 0.03 0.91 ± 0.07
NMRP 12 327 ± 18 111 ± 4 109 ± 6 442 ± 14 0.34 ± 0.03 0.98 ± 0.09
NMRP 13 339 ± 14 112 ± 3 110 ± 4 480 ± 11 0.33 ± 0.02 0.98 ± 0.06
NMRP 14 334 ± 17 123 ± 4 117 ± 5 406 ± 14 0.37 ± 0.03 0.96 ± 0.08
Maximum 639 270 281 595 0.75 1.08
Minimum 73 55 48 134 0.26 0.77
Number of Samples 14

63
Table 4.7: Activity concentrations (Bq kg-1) of untreated Marmul sludge piles (using the HPGe gamma spectroscopy system)
226 228 228 40 228
Sample ID Location 40Q UTM Ra Ra Th K Ra:226Ra 228
Th:228Ra
Easting Northing
MRLP 1 # 319390 2014275 195 ± 20 83 ± 12 67 ± 10 47 ± 43 0.35 ± 0.09 0.81 ± 0.24
MRLP 2 319393 2014288 36 ± 6 9±1 9±1 119 ± 6 0.26 ± 0.09 0.99 ± 0.30
MRLP 3 319385 2014287 42 ± 4 10 ± 1 9±1 135 ± 5 0.24 ± 0.05 0.91 ± 0.20
MRLP 4 319378 2014292 36 ± 4 7±1 8±1 118 ± 5 0.20 ± 0.05 1.07 ± 0.33
MRLP 5 319370 2014292 38 ± 4 9±1 7±2 103 ± 5 0.24 ± 0.06 0.76 ± 0.27
MRLP 6 319365 2014314 125 ± 9 92 ± 3 84 ± 3 639 ± 11 0.73 ± 0.08 0.90 ± 0.06
MRLP 7 319350 2014320 46 ± 6 23 ± 2 17 ± 2 683 ± 11 0.49 ± 0.10 0.76 ± 0.13
MRLP 8 319385 2014271 918 ± 21 845 ± 7 773 ± 7 548 ± 15 0.92 ± 0.03 0.91 ± 0.02
MRLP 9 319392 2014271 1022 ± 24 1557 ± 7 1380 ± 8 359 ± 16 1.52 ± 0.04 0.89 ± 0.01
MRLP 10 27 ± 3 7±1 5±1 84 ± 5 0.26 ± 0.07 0.77 ± 0.18
MRLP 11 146 ± 9 123 ± 3 93 ± 3 653 ± 11 0.84 ± 0.07 0.76 ± 0.04
MRLP 12 196 ± 13 162 ± 3 120 ± 3 720 ± 13 0.83 ± 0.07 0.74 ± 0.04
MRLP 13 3690 ± 60 6036 ± 20 5164 ± 20 519 ± 20 1.64 ± 0.03 0.86 ± 0.01
MRLP 14 2290 ± 40 2211 ± 10 2023 ± 13 477 ± 19 0.97 ± 0.02 0.91 ± 0.01
MRLP 15 1310 ± 30 1444 ± 10 1236 ± 11 443 ± 17 1.10 ± 0.03 0.86 ± 0.01
MRLP 16 166 ± 9 139 ± 3 103 ± 3 601 ± 11 0.84 ± 0.06 0.74 ± 0.04
Maximum 3690 6036 5164 720 1.64 1.07
Minimum 27 7 5 47 0.20 0.74
Number of Samples 16
#
Analysis by NaI portable gamma spectroscopy system

64
 Comparison of Activity Concentrations between Sludge Farms: The data
226 228
presented in this section shows that the Ra and Ra activity concentrations

for the Marmul untreated sludge piles varied significantly (by two and three

orders of magnitude, respectively), compared to the activity concentrations for

the Bahja and Nimr untreated sludge piles, which were within one order of

magnitude (Figure 4.3). Figure 4.3 also illustrates that the two radium isotopes

had a direct proportionality, implying that the encountered increase in gamma

count rate was a result of a simultaneous activity concentration increase for both
226
Ra and 228Ra.

10000

1000
Ra (Bq kg-1)

Marmul
100 Bahja
228

Nimr

10

1
226
1 10
(Bq kg-1)
Ra 100 1000 10000

Figure 4.3: Relation between 226Ra and 228Ra for Marmul, Bahja and Nimr
untreated sludge piles.

65
 The mean ages of Nimr and Marmul untreated sludge piles, as estimated by
228
the Th:228Ra activity ratio, were 4.2 ± 0.3 and 3.6 ± 0.4 years, respectively,

indicating that Nimr and Marmul untreated sludge piles were relatively new and

similar in age. The Bahja untreated sludge piles, on the other hand, were

estimated to be as old as 15 years, which is not unexpected, since the bulk of

high activity untreated sludge piles have been at the farm for quite some time,

and will remain there until an alternative disposal or treatment method is

approved. As a result of these age differences, an inverse relationship was

228
observed between Ra:226Ra and 228
Th:228Ra mean activity ratios for the three

sludge farms (Figure 4.4). On the other hand, as shown in Figures 4.5 (a) and
226 228
(b), no correlation was observed between sludge age and the Ra and Ra

activity concentrations for each individual farm.

1.00

0.75
Ra:226Ra activity ratio

Marmul

0.50
Nimr
228

0.25

Bahja

0.00
0.7 0.9 1.1 1.3 1.5

228
Th:228Ra activity ratio
Figure 4.4: 228Ra:226Ra and 228Th:228Ra mean activity ratios for Bahja, Nimr and
Marmul sludge farms.

66
 10000

Ra activity concentration (Bq kg-1) a

1000

Bahja
Nimr
Marmul

100
226

10
0 2 4 6 8 10
Sludge pile age (years)
10000

b
Ra activity concentration (Bq kg-1)

1000

Bahja
100 Nimr
Marmul

10
228

1
0 2 4 6 8 10
Sludge pile age (years)

Figure 4.5: Sludge pile activity concentration versus age (a) 226Ra, and (b) 228Ra.

67
4.2.5 Radioactivity in treated sludge strips

Gamma spectroscopy results for Bahja, Nimr and Marmul treated sludge

strips are presented in Tables 4.8, 4.9 and 4.10, respectively. The bulk of the

data was collected in the field by the portable NaI gamma spectroscopy system,

while the rest was obtained from analysing samples in the laboratory, using an

HPGe gamma spectroscopy system. As outlined in Chapter 3, Section 3.2, 228Ra

activity concentration was not directly measured in the field, but was calculated
228
from the Th:228Ra activity ratio obtained from laboratory measurements for

samples collected from same locations.

Bahja Sludge Farm: Overall, Bahja’s sludge strips had the lowest mean

(± standard error) activity concentration for 226Ra, 228Ra and 228Th, being 55 ± 3,

14 ± 1 and 11 ± 1 Bq kg-1, respectively. However, these activity concentrations

were still higher than the corresponding ambient soil activity concentrations of

38 ± 5, 11 ± 1 and 9 ± 1 Bq kg-1, respectively (Table 4.2). No localised spots of

higher activity (hotspots: often 1-2 m2 surface area and about 0.5 m deep) were

detected on the treated sludge strips. This was due to the fact that only the

sludge piles with activity concentrations similar to ambient soil radioactivity

were approved for the sludge farming process (refer to discussion in

Section 4.2.4.).

Nimr and Marmul Sludge Farms: Despite dilution by the farming process,
226
the mean and maximum Ra activity concentrations for Nimr and Marmul’s

treated sludge strips were about three and ten times higher than their respective

ambient soil activity concentrations.

68
 Nimr and Marmul’s treated sludge strips were also found to contain

hotspots, even after being mixed with clean soil, which may have been the result

of a non-uniform activity distribution in the sludge. At Nimr sludge farm, a

226 228 228
hotspot was detected on strip 61, with Ra, Ra and Th activity

concentrations of 1340 ± 26, 736 ± 7 and 441 ± 8 Bq kg-1, respectively. At

Marmul sludge farm, two hotspots were detected. The first was on strip 44
226 228 228
(analysed by HPGe), with Ra, Ra and Th activity concentrations of

2080 ± 40, 184 ± 5 and 160 ± 6 Bq kg-1, respectively, and the second on strip 7
226 228
(analysed by portable NaI), with Ra and Th activity concentrations of

1920 ± 54 and 165 ± 16 Bq kg-1, respectively.

It is unlikely that these hotspots will disappear any time soon, since both
228 226
Ra and Ra will require about 7 half lives to decay to ambient soil activity

concentrations. Taking into account the 232Th half life, supported 228Ra found in
228
ambient soil will remain virtually constant while the unsupported sludge Ra

will decay to 0.78 % of its original activity over approximately four decades.

Ra-226, however, has a longer half life, and will require at least 10,000 years to

decay to 0.78 % of its original activity.

In addition, Nimr and Marmul’s ambient soil 228Th:228Ra activity ratios were

1.00 ± 0.14 and 0.83 ± 0.31, respectively, indicating that 228Th and 228Ra were in
232
transient equilibrium with Th. However, at the previously identified hotspots
228 228
for both farms, Th was in disequilibrium with Ra. In Nimr, strip 61’s
228
Th:228Ra activity ratio of 0.6 was characteristic of new sludge activity ratios,
228 228
where Th is in an ingrowth phase with Ra. A similar argument could be

69
made for strips 7 and 44 in Marmul, indicating that these high activity

concentrations were due to the sludge and not the ambient soil.

When calculating the mean and median activity concentrations for the two

farms, these hotspots were excluded from the analysis, due to their potential to

bias the results. As such, the overall results suggest that, on average, Nimr and
226
Marmul sludge Ra activity concentration had been reduced by factors of 4.6

± 1.6 and 3.1 ± 1.9, respectively, as a result of the mixing and tilling process.

Finally, it should be mentioned that 40K activity concentration did not follow

a specific trend for samples collected from the treated sludge strips. The activity

concentrations of 40K for Bahja, Nimr and Marmul were very similar, with mean

(± standard error) values of 175 ± 10, 146 ± 19 and 167 ± 21 Bq kg-1,

respectively.

70
Table 4.8: Activity concentration (Bq kg-1) of Bahja sludge strips
226 228 228 40
Sample ID Location 40Q UTM Ra Ra Th K
Easting Northing
BHJS 005 * 48 ± 6 20 ± 2 15 ± 2 161 ± 6
BHJS 008 * 52 ± 6 18 ± 2 15 ± 2 258 ± 8
BHJS 018 398766 2198993 51 ± 10 13 ± 10 10 ± 4 159 ± 30
BHJS 030 398675 2198899 55 ± 10 13 ± 10 10 ± 4 175 ± 32
BHJS 039 * 47 ± 6 15 ± 2 12 ± 2 164 ± 7
BHJS 043 398775 2198963 68 ± 10 8±7 6±3 175 ± 32
BHJS 065 398736 2198925 58 ± 10 11 ± 9 9±4 163 ± 31
BHJS 070 398698 2198876 71 ± 11 13 ± 10 10 ± 4 107 ± 29
BHJS 073 398682 2198837 52 ± 10 17 ± 12 13 ± 4 191 ± 33
BHJS 076 398659 2198802 37 ± 9 15 ± 11 12 ± 4 178 ± 30
BHJS 078 398637 2198780 62 ± 10 11 ± 9 9±4 172 ± 32
BHJS 080 398617 2198763 63 ± 10 11 ± 9 9±4 198 ± 33
Maximum 71 20 15 258
Minimum 37 8 6 107
Median 54 13 10 174
Mean ± SE 55 ± 3 14 ± 1 11 ± 1 175 ± 10
Standard Deviation 10 3 3 35
Number of Samples 12
* Analysis by HPGe gamma spectroscopy system

71
Table 4.9: Activity concentrations (Bq kg-1) of Nimr sludge strips
226 228 228 40
Sample ID Location 40Q UTM Ra Ra Th K
Easting Northing
NMRS 001 * 133 ± 8 54 ± 2 59 ± 3 200 ± 7
NMRS 024 * 108 ± 7 47 ± 2 41 ± 3 128 ± 7
NMRS 026 * 197 ± 10 103 ± 3 96 ± 3 369 ± 10
NMRS 029 383548 2051927 18 ± 9 22 ± 8 21 ± 6 82 ± 24
NMRS 039 383612 2051829 56 ± 11 19 ± 7 18 ± 5 75 ± 27
NMRS 044a 383648 2051790 22 ± 10 26 ± 9 25 ± 6 102 ± 27
NMRS 044b * 260 ± 10 130 ± 3 136 ± 3 150 ± 7
NMRS 045 * 52 ± 5 17 ± 2 14 ± 2 221 ± 7
NMRS 052 383579 2051742 34 ± 10 20 ± 8 19 ± 5 109 ± 27
NMRS 085 383370 2052107 49 ± 10 12 ± 6 12 ± 4 84 ± 26
NMRS 100 383387 2051795 36 ± 8 8±4 7±3 184 ± 30
NMRS 111 383498 2051667 85 ± 13 29 ± 10 28 ± 6 126 ± 34
NMRS 116 383401 2051590 46 ± 9 12 ± 6 12 ± 4 137 ± 29
NMRS 119 0383375 2051622 37 ± 5 10 ± 1 10 ± 2 118 ± 6
NMRS 126 383332 2051726 17 ± 9 23 ± 8 22 ± 6 132 ± 27
NMRS 143 383291 2051664 32 ± 8 12 ± 6 12 ± 4 113 ± 26

72
Table 4.9 (Continued): Activity concentrations (Bq kg-1) of Nimr sludge strips
226 228 228 40
Sample ID Location 40Q UTM Ra Ra Th K
Easting Northing
Maximum 260 130 136 369
Minimum 17 8 7 75
Median 47 21 20 127
Mean ± SE 74 ± 18 34 ± 9 33 ± 9 146 ± 19
Standard Deviation 69 35 36 73
Number of Samples 16
* Analysis by HPGe gamma spectroscopy system

73
Table 4.10: Activity concentrations (Bq kg-1) of Marmul sludge strips
226 228 228 40
Sample ID Location 40Q UTM Ra Ra Th K
Easting Northing
MRLS 005 319306 2014175 38 ± 10 16 ± 6 18 ± 5 119 ± 28
MRLS 011 319230 2014186 66 ± 12 17 ± 7 19 ± 5 54 ± 27
MRLS 013 319161 2014080 63 ± 11 13 ± 6 15 ± 5 114 ± 30
MRLS 015 * 9.5 ± 0.7 1.9 ± 0.2 2.3 ± 0.2 16 ± 1
MRLS 018 319120 2014219 62 ± 12 25 ± 8 28 ± 6 39 ± 27
MRLS 019 * 414 ± 13 117 ± 3 138 ± 4 188 ± 9
MRLS 020 * 295 ± 19 76 ± 3 96 ± 4 467 ± 13
MRLS 021 319058 2014135 56 ± 11 19 ± 7 21 ± 6 58 ± 27
MRLS 024 319079 2014233 52 ± 12 24 ± 8 27 ± 6 53 ± 27
MRLS 025a 319352 2014140 153 ± 17 28 ± 9 31 ± 7 141 ± 40
MRLS 025b 319352 2014140 181 ± 16 9±5 10 ± 4 240 ± 44
MRLS 027 * 175 ± 9 60 ± 3 65 ± 3 455 ± 11
MRLS 031 * 79 ± 7 23 ± 2 26 ± 2 163 ± 6
MRLS 033 * 205 ± 11 116 ± 3 116 ± 4 313 ± 10
MRLS 046 * 455 ± 15 121 ± 4 109 ± 5 264 ± 9
MRLS 062 * 115 ± 8 61 ± 2 69 ± 2 166 ± 7
MRLS 069 319026 2014173 80 ± 12 15 ± 6 16 ± 5 284 ± 39
MRLS 102a 319037 2014148 67 ± 15 51 ± 14 56 ± 9 214 ± 40

74
Table 4.10 (Continued): Activity concentrations (Bq kg-1) of Marmul sludge strips
226 228 228 40
Sample ID Location 40Q UTM Ra Ra Th K
Easting Northing
MRLS 102b 319042 2014179 92 ± 20 100 ± 22 111 ± 13 204 ± 47
MRLS 102c 319046 2014183 180 ± 24 130 ± 27 144 ± 15 137 ± 53
MRLS 112 319143 2014210 56 ± 11 21 ± 8 24 ± 6 35 ± 26
MRLS 115 319174 2014200 22 ± 10 23 ± 8 25 ± 6 166 ± 30
MRLS 118 319202 2014078 59 ± 11 15 ± 6 16 ± 5 110 ± 29
MRLS 148 319125 2014094 27 ± 11 31 ± 10 34 ± 7 103 ± 29
MRLS 183 319261 2014182 37 ± 12 31 ± 10 34 ± 7 54 ± 27
MRLS 186 319091 2014110 42 ± 9 12 ± 5 13 ± 4 79 ± 25
MRLS 189 319199 2014192 44 ± 10 15 ± 6 16 ± 5 93 ± 27
MRLS 192 319318 2014095 118 ± 13 5±3 6±3 205 ± 38
MRLS 193 319283 2014108 121 ± 14 11 ± 5 12 ± 4 197 ± 38
Maximum 455 130 144 467
Minimum 9.5 1.9 2.3 16
Median 67 23 26 141
Mean ± SE 116 ± 21 41± 7 45 ± 8 163 ± 22
Standard Deviation 110 39 42 114
Number of Samples 29
* Analysis by HPGe gamma spectroscopy system

75
4.3 Bahja NORM store yard
226
As mentioned in Section 4.2, any sludge or scale with a Ra activity

concentration higher than 1 kBq kg-1 is transported to the Bahja NORM storage

facility, in order to safely segregate the NORM contaminated scales and sludge

until a suitable disposal method is found. The yard is also used to store

decommissioned oil and gas distribution pipes before they are sent for cleaning,

along with a number of submersible electrical pumps, well heads and other

surface equipment.

The Bahja store yard consists of approximately 6 acres of flat compacted

land, surrounded by a boundary fence, with a locked gate. Figure 4.3 (a) shows

some of the sludge barrels, originally stored in Zuliya NORM store yard,

located some 70 km northwest of Bahja (refer to map in Chapter 2, Figure 2.1),

which were relocated to the Bahja NORM store yard in February 2007. At the

Bahja store yard, some of the oily sludge is also stored in one of two storage

pits, lined by a geo-textile material, designed to prevent seepage into the

surrounding earth (Figure 4.3 (b)). These pits are about 1 m deep, 10 m wide

and 100 m long. At the time of our last site visit (21 April – 8 May 2007), there

were approximately 5,000 decommissioned gas pipes (with a length and an

inner diameter of 8 m and 9 cm, respectively) and 20 decommissioned oil pipes

(of varying lengths and shapes, with an inner diameter of 35 cm) in the store

yard (Figure 4.3 (c)).

76
 (a) (b) (c)

Figure 4.6: NORM store yards:

(a) Sludge stored in 120 steel barrels with 226Ra activity content ≥ 1 kBq kg-1 (Zuliya store yard)
(b) Oily sludge in one of the two geo-textile lined pits (Bahja store yard), and
(c) Oil and gas pipes and other oil processing equipment contaminated with NORM at (Bahja store yard).

77
4.3.1 Oil industry scales

4.3.1.1 Oil scale formation and removal

The initial extraction of oil from the reservoir is usually water-free,

however, as the well ages and more oil is extracted from the formation rock, the

temperature and pressure in the reservoir decreases and the natural water present

in the reservoir will begin to be co-produced with the oil (Smith, 1987).

Subsequent to extraction, the dissolved radium present in the produced water is

co-precipitated with calcium and barium, in the form of carbonates and

sulphates, resulting in the formation of hard and highly insoluble scale deposits

on the interior walls of both the pipes, and other production equipment (Testa et

al., 1994, Hamlat et al., 2001, Godoy and Petinatti da Cruz, 2003, Paschoa,

2003, Hamlat et al., 2003b, Hamilton et al., 2004, Al-Masri and Aba, 2005,

Bader, 2006). The predominant scale constituents are those of calcium

carbonate (CaCO3) and calcium and barium sulphate (Ca/BaSO4), however,

barium and magnesium carbonate (Ba/MgCO3), along with strontium sulphate

(SrSO4) may also be found to a lesser degree (Hamilton et al., 2004) . Rn-222
220
(T½: 3.824 days, alpha energy 5.49 MeV) and Rn (T½: 55.6 seconds, alpha

energy 6.29 MeV), along with their progeny, may also be exhaled from scales

and/or build up in the crude oil and gas streams (Rood et al., 1998, Worden et

al., 2000). Like barium and strontium, radium is an alkaline earth metal that

belongs to the group II elements in the periodic chart, and as such, it also

displays similar chemical properties.

78
 According to Wilson and Scott (1992), the scale formation process occurs in

three stages. Firstly, a scale molecule is formed, when there is a supersaturation

or other chemical disequilibrium in the environment. Secondly, these molecules

come together, forming microcrystalline nuclei that grow and coalesce to form

clusters. When the clusters reach a specific size, precipitation takes place.

Finally, the precipitate adheres to the inner walls of the production equipment,

including the well fluid handling system, down-hole pipes, well heads,

subsurface safety valves, manifolds, separators, oil coolers and produced water

distribution pipes. Although the sticking mechanism is not well understood,

initial surface nucleation seems to be an important factor, before the

precipitation can take place.

In addition to increasing production costs, as a result of the maintenance and

downtime associated with their removal, these scales also reduce efficiency by

clogging valves, restricting flow and damaging equipment (IAEA, 2003,

Hamilton et al., 2004). The removal of scale not only requires time and money,

but also significant expertise, especially since most scales are NORM

contaminated. As such, appropriate radiation protection measures should be

enforced according to the method adopted for scale removal. In Oman, PDO

have approved two main methods of scale removal. Initially, partially clogged

flow line pipes are physically cleared of solid scale deposits while still in

operation, using a process called ‘pigging’. This process utilises a rotating

plastic or rubber plug, termed a ‘pig’, which is launched upstream of the main

flow and then recovered (along with the removed scale) using a ‘pig trap’,

79
located further down-stream (IAEA, 2003). The removed scale/sludge is then

transported to the nearest sludge farm for storage and/or disposal.

When the flow lines become completely clogged and pigging is no longer an

option, the pipes are decommissioned and transported to Bahja NORM store

yard. It is then possible for scale build-up to be removed, through the

application of a mechanically controlled metal rod, used to break up the scale.

This would then be followed by the application of high pressure water jets

(1500-2500 bar), designed to clear the broken scale from the pipes (Al-Masri

and Aba, 2005). However, at the time of writing this thesis, PDO was still in the

process of finding an appropriate contractor to build a decontamination facility

for the removal of these scales, and until such time as this occurs, these pipes

and contaminated equipment are unable to be re-used or melted down and

recycled.

In addition to the number of other scale decontamination and disposal

options discussed by Rood et al. (1998), IAEA (2003) and Hamilton et al.

(2004), IAEA (2003) also discussed the possibility of preventing scale

precipitation, by introducing scale-inhibiting chemicals into the seawater

injection systems, which would act to prevent sulphate and carbonate scale

deposition. The prevention of scale build-up would mean that the radium

isotopes would actually move through production system, and would only be

found in the final produced water by-product. However, this theory was

challenged by several authors (Rajaretnam and Spitz, 2000, Shawky et al.,

80
2001), who argued that scale prevention or remediation processes are not only

difficult, but also very expensive to manage.

4.3.1.2 Radioactivity in oil scales

Seven oil scale samples were collected from decommissioned flow line

pipes (35 cm in diameter), originally used to pump produced water from the

separator tanks (see Chapter 3, Section 3.2.1 and 3.2.2 for details on sampling

and measurement procedures). The radioactivity of these samples was then

analysed using the HPGe system and the full range of gamma spectroscopy

results for the scale samples are presented in Table 4.12.

Radium 226 and 228: The main isotopes found during this analysis were
226 238 228
Ra (T½: 1602 years; U primordial series), and to a lesser degree Ra

(T½: 5.75 years; 232Th primordial series), with the highest activity concentrations
226 228
for Ra and Ra being about 500 times higher than the mean ambient soil

activity concentrations found in the south of Oman (Table 4.2).

This finding can be explained by the fact that radium is somewhat soluble in

water, when placed under the high temperatures and pressures found in
226
petroleum reservoirs, Ra tends to leach into co-existing brines or formation

water (Rajaretnam and Spitz, 2000, Shawky et al., 2001). Upon 226Ra decay, the
222
product, Rn, migrates back into the organic liquid and natural gas phases

(Jerez Vegueria et al., 2002b). In contrast, uranium and thorium are part of the

rock matrix core, and since neither are highly soluble in water, only trace

81
 238 232 228 210 210
amounts of U, Th, Th, Pb and Po are generally found in reservoir

fluids (White and Rood, 2001).

226 228 228

Overall, Ra, Ra and Th activity concentrations ranged between

3.4-17.3, 1.4-4.3 and 1.4-5.7 kBq kg-1, respectively, and Ra-228 activity
226
concentrations were less than Ra values, with a mean (± standard error) for
228
Ra:226Ra activity ratio of 0.307 ± 0.026. A number of other studies also

reported radium activity in scales. For example, in Malaysia, Omar et al. (2004)

reported maximum activity concentrations of 434 and 479 kBq kg-1 for 226
Ra
228
and Ra, respectively, while Godoy and Petinatti da Cruz (2003) reported

activity concentrations of 19.1-323 kBq kg-1 for 226Ra and 4.21-235 kBq kg-1 for
228
Ra, in Brazil. Al-Masri and Aba (2005) also investigated activity

concentrations for oil scales in the Republic of Syria, and found maximum

(mean) radium isotope activity concentrations of 1520(174), 868(91) and

780(67) kBq kg-1 for 226Ra, 228Ra and 224Ra, respectively.

While the radium activity concentration values reported in this study were

within the typical range reported internationally of 0.1-15,000 kBq kg-1 (Jonkers

et al., 1997, IAEA, 2003), it was found that the activity concentrations observed

in Oman were somewhat lower than the values reported in the above mentioned

studies. This could either be attributed to the difference in Oman geological

formations to those found elsewhere in the world, or an indication that

radioactive scale formation is still in its early stages, since older reservoirs tend

to have higher produced water to crude oil volume ratio, and hence higher

quantity of NORM (Rood et al., 1998). Another possible reason for the

82
discrepancy is that the scale samples collected in this study were taken from the

available downstream pipes, used for handling produced water once it was

separated from the crude oil. This can be explained by other reported findings,

which suggest that radium isotopes activity concentrations are higher in up-

stream scales that form between the reservoir and the well head, compared to

down-stream scales that form in the distribution pipes (Hamilton et al., 2004,

Al-Masri and Aba, 2005).

227
Actinium 227: In addition to radium isotopes, unsupported Ac (T½:
235
21.77 years; U primordial series) was also detected in the oil scale samples.

Whilst no other activity concentrations for 227Ac in oil scales have been reported

to date, its association with naturally occurring brines in the environment has

been reported by a number of authors, such as Dickson (1991), Lieser et al.

(1999), and Martin and Akber (1999). For example, Martin and Akber (1999)
227
studied Ac behaviour in aqueous solutions containing seepage from the
227
tailings impoundments of a uranium mine, by looking at Ac:223Ra ratio, and
223
came to the conclusion that not all of the Ra in solution was supported by
227 227
Ac, due to the absorption of the intermediate radionuclide Th

(T½: 18.7 days).

In contrast, results for the solid scales analysed in this research showed
223
Ra (T½: 11.4 days) in equilibrium with 227Ac at the time of measurement, and

since our samples were collected from pipes which had been decommissioned
223
several years prior, any unsupported Ra would have been completely
223
decayed, indicating that the only possible source of the detected Ra was the

83
 227 227
disintegration process of Ac. This newly quantified presence of Ac in oil

and gas scales is highly important, since it can not only pose a significant

radiological hazard, but it also has a higher committed effective dose coefficient

for inhalation and ingestion compared to the other radionuclides found in scales

and sludge (Table 4.11).

Table 4.11: Committed effective dose coefficients (µSv Bq-1) of selected

radionuclides likely to be present in petroleum scales (ICRP68)
227 228 226 210
Mode of Radioisotope Ac Ra Ra Pb +
210
Entry ↓ → Po

Inhalation for 1 µm AMAD 540 2.6 3.2 1.5

Ingestion 1.1 0.67 0.28 0.92

227
As such, the presence of Ac in oil scales is thought to be a result of its

affinity to the brines found in oil reservoirs, which would then allow it

precipitate with the other minerals on the internal surface of the pipes. The

maximum 227Ac activity concentration, of 123 Bq kg-1, was more than 70 times

higher than the theoretically calculated ambient soil value of 1.7 Bq kg-1.

Lead 210: The oil scale samples analysed in this study were collected from

pipes decommissioned in 1999. Considering that these pipes had been in service

for 10 years prior to decommission, this means that the scales would have been
210
in the pipes for at least 18 years. As such, assuming zero Pb activity at the
210
time the scales were forming, the expected Pb:226Ra activity ratio would be

0.42. Moreover, dating the oil scales using the 228Th:228Ra activity ratio gave an
210
average age of 15 years, indicating that the expected Pb:226Ra activity ratio

was 0.36. However, both of these calculations were significantly lower than the

84
 210
actual mean (± standard error) for Pb:226Ra activity ratio measured in this

study, being 0.64 ± 0.08. This discrepancy indicates that there was higher than
210
expected Pb in the oil scale samples collected in this study, possibly brought

to the surface from the reservoir rock by the produced water.

85
Table 4.12: Activity concentrations (Bq kg-1) of oil scale samples
226 210 228 228 227 40 228
Sample ID Ra Pb Ra Th Ac K Ra:226Ra 228
Th:228Ra 210
Pb:226Ra

FHDOS 1 4360 ± 50 3060 ± 610 1550 ± 10 2070 ± 380 40 ± 7 < 28 0.356 ± 0.006 1.34 ± 0.25 0.70 ± 0.15
FHDOS 2 13000 ± 100 4990 ± 1410 3230 ± 20 4800 ± 720 68 ± 14 < 54 0.248 ± 0.003 1.49 ± 0.23 0.38 ± 0.11
FUDOS 3 3380 ± 40 3310 ± 470 1360 ± 10 1930 ± 390 47 ± 7 < 27 0.402 ± 0.008 1.42 ± 0.30 0.98 ± 0.15
FHDOS 4 11800 ± 100 6450 ± 1490 3100 ± 20 4950 ± 740 67 ± 13 < 52 0.263 ± 0.004 1.60 ± 0.25 0.55 ± 0.13
FHDOS 5 6340 ± 60 4330 ± 870 2250 ± 10 2920 ± 420 34 ± 9 < 33 0.355 ± 0.005 1.30 ± 0.19 0.68 ± 0.14
FHDOS 6 17300 ± 100 7590 ± 1640 4310 ± 20 6810 ± 950 123 ± 17 < 65 0.249 ± 0.003 1.58 ± 0.23 0.44 ± 0.10
FHDOS 7 6380 ± 50 4720 ± 570 1740 ± 10 2610 ± 440 71 ± 9 < 32 0.273 ± 0.004 1.50 ± 0.26 0.74 ± 0.10
Maximum 17300 7590 4310 6810 123 0.402 1.60 0.98
Minimum 3380 3060 1360 1930 34 0.248 1.30 0.38
Median 6380 4720 2250 2920 67 0.273 1.49 0.68
Mean ± SE 8940 ± 2110 4920 ± 670 2510 ± 440 3730 ± 750 64 ± 12 0.307 ± 0.026 1.46 ± 0.05 0.64 ± 0.08
Standard
Deviation 5160 1630 1080 1830 30 0.063 0.11 0.20
Number of
Samples 7

86
4.3.2 Gas industry scales

4.3.2.1 Gas scale formation and removal

Radon is a noble gas, also known to be soluble in organic matter, and its

association with natural gas streams has been known for almost 100 years

(Satterly and McLennan, 1918). From a radiological hazard point of view, 220Rn

(Ra-228 progeny, T½: 55.6 seconds) does not pose as high a risk in oil industry,
222
as Rn (Ra-226 progeny, T½: 3.824 days), the reason being that the former

only has a few short-lived progeny, whereas the latter has two long-lived
210 210
progeny, Pb and Po, with half-lives of 22.3 years and 138.4 days,

respectively.

210
The precipitation of Pb results in a thin radioactive film forming on the

internal walls of gas pipes, pumps and vessels, with a reported specific activity

higher than 1 kBq g-1 (Hamlat et al., 2003a, Al-Masri and Shwiekani, 2008).

Although Pb-210 has a soft gamma of 46.5 keV, which cannot even be detected

by a conventional dose rate meter outside the pipes, it has an extremely high

toxicity value if inhaled or ingested via dust particles, during plant maintenance.
210
Both stable lead and Pb are known to be mobilised from the reservoir rock,

however the mechanism by which this occurs is not yet well understood

(Jonkers et al., 1997, IAEA, 2003). Condensates derived from natural gas have
210 210
also shown elevated Po relative to its grandparent Pb, suggesting a direct

emanation from the reservoir rock (IAEA, 2003).

87
 222
In addition, because Rn has a boiling point between ethane and propane,
222
unsupported Rn is also known to migrate with the ethane and propane
222
fractions of the natural gas stream. As such, high levels of Rn daughters

(210Pb, 210
Bi and 210
Po) are often found in the internal walls of ethane and

propane processing pumps and vessels.

4.3.2.2 Radioactivity in gas scales

The radioactivity of gas scale samples was also analysed using the HPGe

system. Scale samples were collected from 12 pipes, according to the sampling

and measurement procedures outlined in Chapter 3, Section 3.2.1 and 3.2.2. The
210
main gamma emitting radionuclides identified during the analysis were Pb,
227
Ac, 40K and 226Ra. The full range of gamma spectroscopy results are shown in

Table 4.13.

210
Radium isotopes and Lead 210: The Pb activity concentration of the

samples ranged from 0.959-66.4 kBq kg-1, with a mean value of

30.56 ± 7.83 kBq kg-1, however the mean 226

Ra activity concentration of

75 ± 10 Bq kg-1 was too low to support such activity. This suggests that the high
210
Pb radioactivity may be the result of 222Rn decay, which is known to migrate
226
with the gaseous organic phase. While the activity ratio of Ra:210Pb ranged

between 1.2 x 10-3 - 2.3 x 10-2, with a mean of (7.5 ± 2.5) x 10-3, Jonkers et al.
210 226
(1997) reported detection of Pb activity concentrations higher than Ra,

with a 226Ra:210Pb activity ratio of 0.1. As such, the ratios reported in this study

were approximately two orders of magnitude less than Jonkers et al. (1997)
228 226
ratio. Mean Ra activity concentration was four times lower than mean Ra

88
 226
activity concentration. Gas scales mean activity concentrations for both Ra

and 228Ra were two times higher than in ambient soils.

Thorium 228 and Potassium 40: Th-228 activity concentrations were

below HPGe system’s MDA, and therefore the data presented in Table 4.16 for
228 224 212
Th, are the error weighted averages derived from its progeny; Ra, Pb,
212
Bi and 208Tl. This resulted in relatively higher uncertainties in the 228Th:228Ra

activity ratios in the gas scales compared to oil scales. The mean (± standard

error) 228Th:228Ra activity ratio of 1.47 ± 0.12 results in an average gas scale age

of approximately 16 years.

226
Actinium 227: As mentioned in Section 4.2.2, the mean Ra activity

concentration in ambient soils is 34 Bq kg-1. Assuming equilibrium and uranium

227
mass balance, this would indicate an average Ac activity concentration of

1.7 Bq kg-1 in ambient soils. Higher than ambient 227

Ac activity concentrations

were detected in 10 out of the 12 gas scale samples, ranging from 4-181 Bq kg-1.
227
Hence the maximum activity concentration of Ac in the gas scales was more

than 100 times higher than the ambient soil value. To date, the only other
227
numerical value reported for Ac activity concentration in gas scale was

2.5 Bq g-1, published by Kolb and Wojcik (1985).

89
Table 4.13: Activity concentrations (Bq kg-1) of gas scale samples
226 210 228 228 227 40 228
Sample ID Ra Pb Ra Th Ac K Ra:226Ra 228
Th:228Ra 226
Ra:210Pb

ZULGS 1 114 ± 25 66405 ± 882 25 ± 2 39 ± 5 69 ± 4 73 ± 7 0.22 ± 0.06 1.58 ± 0.34 (1.7 ± 0.4)x10-3
ZULGS 2 125 ± 13 49013 ± 703 26 ± 2 41 ± 5 71 ± 4 89 ± 7 0.21 ± 0.04 1.58 ± 0.31 (2.6 ± 0.3)x10-3
ZULGS 3 33 ± 6 6241 ± 200 7.8 ± 1.1 7.4 ± 2.1 5±1 347 ± 8 0.24 ± 0.08 0.95 ± 0.40 (5.3 ± 1.1)x10-3
ZULGS 4 51 ± 21 43377 ± 633 5.6 ± 1.0 7.6 ± 2.0 9±4 26 ± 4 0.11 ± 0.07 1.37 ± 0.60 (1.2 ± 0.5)x10-3
ZULGS 5 53 ± 13 < 541 < 6.3 - < 6.9 76 ± 15 - - -
ZULGS 6 83 ± 12 5643 ± 353 19 ± 2 41 ± 5 24 ± 3 157 ± 11 0.23 ± 0.06 2.20 ± 0.58 (1.5 ± 0.3)x10-2
ZULGS 7 84 ± 15 5991 ± 538 24 ± 4 42 ± 7 21 ± 4 212 ± 17 0.28 ± 0.10 1.76 ± 0.62 (1.4 ± 0.4)x10-2
ZULGS 8 82 ± 15 9110 ± 457 16 ± 3 13 ± 4 65 ± 4 236 ± 14 0.20 ± 0.07 0.80 ± 0.37 (9.0 ± 2.1)x10-3
ZULGS 9 < 32 54039 ± 710 6.1 ± 0.9 9.9 ± 2.2 < 7.6 30 ± 4 - 1.65 ± 0.59 -
ZULGS 10 84 ± 13 52678 ± 658 24 ± 2 35 ± 5 181 ± 4 98 ± 7 0.28 ± 0.07 1.48 ± 0.32 (1.6 ± 0.3)x10-3
ZULGS 11 22 ± 4 959 ± 108 2.3 ± 0.6 2.9 ± 1.3 4±1 61 ± 4 0.11 ± 0.05 1.26 ± 0.90 ( 2.3 ± 0.7)10-2
ZULGS 12 92 ± 24 42716 ± 502 32 ± 3 48 ± 5 11 ± 5 190 ± 10 0.35 ± 0.12 1.51 ± 0.30 (2.2 ± 0.6)x10-3
Maximum 125 66405 32 48 181 347 0.35 2.20 2.3 x 10-2
Minimum 22 959 2.3 2.9 4 26 0.11 0.80 1.2 x 10-3
Median 83 42716 19 35 22 94 0.22 1.51 3.9 x 10-3
Mean ± SE 75 ± 10 30561 ± 7830 17 ± 3 26 ± 6 46 ± 18 133 ± 29 0.22 ± 0.02 1.47 ± 0.12 (7.5 ± 2.5)x10-3
Standard 32 24759 10 18 55 97 0.07 0.38 7.4 x 10-3
Deviation
Number of 12
Samples

90
4.3.3 Comparison between oil and gas scales

Figure 4.7 shows a comparison between average radionuclide activity

concentration for the oil and gas scales analysed in this study. Ac-227 activity

concentrations for both oil and gas scales were within the same order of
226
magnitude, whilst the Ra activity concentration for oil scales was two orders
210
of magnitude higher than for gas scales. In contrast, the Pb activity

concentration for gas scales was one order of magnitude higher than for oil
226
scales. The Ra:210Pb activity ratio of gas scales, being (7.5 ± 2.5) x 10-3,
210
supports the theory outlined earlier in this chapter, that excess Pb was

transported in the natural gas stream as a result of 222Rn decay, as well as being
210
directly mobilised from the reservoir rock. Similarly, the Pb:226Ra activity

ratio for oil scales, being 0.64 ± 0.08, indicates that the ratio is higher than
210 226
expected by Pb ingrowth from Ra decay, given the scale age, suggesting

direct mobilisation of 210Pb from the reservoir rock by the produced water.

91
 100

Activity concentration (Bq g-1)

10

Gas scales
1
Oil scales

0.1

0.01
Ac-227 Ra-226 Pb-210 Ra-228 Th-228 K-40

Radionuclide

Figure 4.7: Average activity concentrations for radionuclides found in oil and gas
scales.

228 228
Although Ra and Th activity concentrations for oil scales were two

orders of magnitude higher than for gas scales, the 228Th:228Ra mean (± standard

error) activity ratios of 1.46 ± 0.05 and 1.47 ± 0.12, respectively, indicate a

similarity in their average age. While the mean (± standard error) for gas scales
40
K was 133 ± 29 Bq kg-1, oil scale 40
K activity concentrations were less than

the HPGe system’s MDA.

4.3.4 Radioactivity in the sludge stored in barrels

According to PDO’s Health, Safety and Environment Specifications (2005),

226
NORM contaminated sludge, with a Ra activity concentration equal to or

higher than 1 kBq kg-1, is separated from the rest of the sludge, packed in steel

92
barrels and transported to the Bahja NORM store yard as soon as possible. At

the time of our last visit to the site (21 April – 8 May 2007), there were more

than 200 barrels stored at the Bahja NORM store yard, and this number will

continue to increase, until a suitable disposal method is found for this

radioactive oily sludge.

Barrel surface dose rates of up to 40 µSv h-1 were encountered during the

field work, with six sludge samples collected from the barrels and taken back to

the laboratory for further analysis (see Chapter 3, Section 3.2.1 and 3.2.2 for

details on sampling and measurement procedures). Single samples were also

collected from separate barrels containing beads and sand. All samples were

analysed using the HPGe system and the results are shown in Table 4.14.

226
Radium and Thorium Isotopes: Ra radioactivity concentrations for the

barrel stored sludge varied over a wide range of at least two orders of

magnitude. The highest activity concentrations were 223 kBq kg-1 for 226
Ra,

34 kBq kg-1 for 228

Ra and 45 kBq kg-1 for 228
Th, which were similar to values

measured in Brazil, reported by Matta et al. (2002), which were up to

331 kBq kg-1 for 226

Ra, 245 kBq kg-1 for 228
Ra and 272 kBq kg-1 for 228
Th

(Table 4.15). Possible reasons for this difference have already been outlined in

Section 4.3.1.2.

Gazineu et al. (2005) also reviewed some of the existing international data
226 228
for Ra and Ra activity concentrations in sludge samples from various oil

93
exploration operators. Table 4.15 provides a summary of their findings,

alongside the findings from Matta et al. (2002) and the findings from this study.

Table 4.14: Range of sludge 226Ra and 228Ra activity concentrations (kBq kg-1) for
oil exploration operations of several countries of the world

Country Material 226

Ra 228
Ra

Brazil * sludge 0.13 – 331 0.01 – 245

Brazil sludge 0.36 – 367 0.25 – 343

Norway sludge 0.1 – 4.7 0.1 – 4.6

Algeria sludge 0.069 – 0.393 -

Oman ** sludge (in store) 1.7 – 223 1.2 – 34.4

Oman ** sludge (separator tank) 0.36 – 0.99 0.14 – 0.45

Oman ** sludge (piles) 0.027 – 5.670 0.007 – 6.036

* Matta et al. (2002); ** This study; All other data are from Gazinue et al.

227
Actinium 227: Both the mean and maximum Ac activity concentrations,

of 188 Bq kg-1 and 614 Bq kg-1, were two orders of magnitude higher than our

theoretically calculated value of 1.7 Bq kg-1, for Oman’s ambient soils. In

addition the mean is an order of magnitude higher than both oil and gas scale

averages. However, the maximum activity concentration obtained was four

times less than the single value reported by Kolb and Wojcik (1985), for a

CaCO3 gas field scale in North Germany.

228
Further, the Th:228Ra activity ratio indicates that the sludge found in the

barrels was quite new, with a mean age of 4 years (except for sample 6, which

gave an average age of 8.3 years).

94
Table 4.15: Activity concentrations (Bq kg-1) for sludge stored in barrels
226 228 228 227 40 228
Sample ID Ra Ra Th Ac K Ra:226Ra 228
Th:228Ra

BHJB 1 14000 ± 100 10489 ± 32 8975 ± 37 141 ± 18 336 ± 32 0.74 ± 0.01 0.88 ± 0.01
BHJB 2 1700 ± 30 1212 ± 10 916 ± 9 286 ± 8 1480 ± 30 0.70 ± 0.02 0.80 ± 0.01
BHJB 3 5560 ± 69 3747 ± 18 3320 ± 20 40 ± 20 952 ± 33 0.66 ± 0.01 0.92 ± 0.01
BHJB 4 2000 ± 40 1478 ± 10 1218 ± 11 15 ± 7 953 ± 23 0.73 ± 0.02 0.86 ± 0.01
BHJB 5 6700 ± 70 4639 ± 20 4041 ± 21 31 ± 17 765 ± 25 0.68 ± 0.01 0.91 ± 0.01
BHJB 6 223000 ± 355 34413 ± 47 44639 ± 83 614 ± 66 < 170 0.15 ± 0.00 1.30 ± 0.00
Beads * 38012 ± 131 39491 ± 39 29109 ± 36 247 ± 24 < 80 1.04 ± 0.00 0.74 ± 0.00
Sand * 35386 ± 162 69406 ± 58 53653 ± 516 440 ± 49 324 ± 54 1.96 ± 0.01 0.77 ± 0.01
Maximum 223000 34413 44639 614 1480 0.74 1.30
Minimum 1700 1212 916 15 336 0.15 0.80
Median 6130 4193 3680 91 952 0.69 0.89
Mean ± standard error 42160 ± 39670 9330 ± 5696 10518 ± 7587 188 ± 104 897 ± 206 0.61 ± 0.10 0.94 ± 0.08
Standard deviation 88705 12738 16965 232 412 0.22 0.18
Sample count 8
* Not included in the sum calculations

95
4.4 Radioactivity in the sediments of Al-Noor
evaporation ponds
Like many other industrial operations, the petroleum industry makes use of

ponds, trenches or pits to store or evaporate liquid wastes generated during oil

production. Al-Noor evaporation pond (Figure 4.7) is used for the evaporation

of produced water generated by the dehydration of crude oil at nearby Al-Noor

station (refer to map in Chapter 2, Figure 2.1). Al-Noor evaporation pond is

secured by a boundary net with a lockable gate; it has an area of 14,400 m2, a

depth of about 1.5 m and is lined by high density polyethylene thermoplastic.

The pond is comprised of two sections (Section 1 and Section 2),

interconnected by four channels, which allow water to flow from Section 1 to

Section 2. Approximately 10 m3 of produced water is pumped into Section 1 on

a daily basis, and this waste water is contaminated by NORM, heavy metals,

volatile organic compounds, polycyclic aromatic hydrocarbons and other toxic

compounds. Evaporation concentrates the NORM activity content of the

produced water, which then crystallises and eventually leads to scale formation

on the ponds internal walls. Six samples were collected from the pond for

analysis, according to the sampling and measurement procedures described in

Chapter 3, Section 3.2.1 and 3.2.2. The radioactivity of these sediment samples

was analysed using the HPGe system.

96
 This image is not available online.
Please consult the hardcopy thesis
available from the QUT Library

Figure 4.8: Section 2 of Al-Noor evaporation pond [picture courtesy of

Mohammad Al-Masri].

227
During this study, Ac was detected for the first time in oil scales and

sludge, however it was not detected in produced water evaporation pond

sediments, because it is most likely transported as a vector and deposited with

238
scale before reaching the ponds. The samples were found to contain both U
232 226 228
and Th progeny, with maximum Ra and Ra activity concentrations of

5.26 and 0.58 kBq kg-1, respectively (Table 4.16). This activity was localised at
226
the drainage point of the pond. The median and maximum Ra activity

concentrations were also more than 10 and 170 times higher than the Al-Noor

ambient soil radioactivity, respectively.

At the time of our last visit to the site (21 April – 8 May 2007) the pond had

also accumulated a 50 cm thick layer of sediment. At the time of deposition, this

97
 228
sediment was found to have a mean Ra:226Ra activity ratio of 0.12. This

corresponded to a 232Th:238U mass ratio of 0.36, which is approximately half the

value obtained for nascent sludge at Nimr (0.73), which may serve to illustrate

the difference in geological formation fingerprints between the two regions.

98
Table 4.16: Activity concentrations (Bq kg-1) of Al-Noor evaporation pond soil sediments
226 228 228 40 228
Sample ID Ra Ra Th K Ra:226Ra 228
Th:228Ra

NOR 1 5260 ± 48 585 ± 9 188 ± 6 193 ± 20 0.11 0.32

NOR 2 354 ± 13 35 ± 2 17 ± 2 109 ± 8 0.10 0.48
NOR 3 119 ± 7 10 ± 1 5±1 30 ± 5 0.08 0.46
NOR 4 743 ± 16 77 ± 3 31 ± 4 429 ± 13 0.10 0.40
NOR 5 379 ± 12 46 ± 2 8±3 379 ± 9 0.12 0.17
NOR 6 107 ± 6 13 ± 2 5±2 837 ± 12 0.12 0.40
Maximum 5260 583 205 837 0.12 0.48
Minimum 107 10 5 30 0.08 0.17
Median 367 41 13 286 0.11 0.40
Mean ± standard error 1160 ± 904 127 ± 100 46 ± 35 330 ± 131 0.11 ± 0.01 0.37 ± 0.05
Standard deviation 2022 225 79 292 0.01 0.11
Sample number 6

99
4.5 Discussion and conclusions
This chapter outlined the radioactivity concentrations found in oilfields of

the Southern Oman Directorate, where the radioactivity of untreated and treated

sludge, oil and gas scales, barrel stored sludge and evaporation pond sediment,

was assessed using both in-situ and laboratory gamma spectrometers. This is the

first comprehensive survey of radioactivity concentrations to be conducted for

the petroleum industry, in the Sultanate of Oman, and it is also the first ever

study to report the detection of 227Ac in oil sludge and in both oil and gas scales.

210
Ac-227 half life (21.8 years) is similar to that of Pb (22.3 years), but

because it is unsupported it would decay to ambient levels in seven to nine half

lives. On the other hand, the 226Ra supported 210Pb is a longer term radiological

hazard. Because once it reached secular equilibrium with its parent radionuclide

by ingrowth in about 100 years, it would decay at a 226Ra half life of 1602 years.

This study successfully made use of a portable NaI(Tl) gamma spectroscopy

226 228
system for measuring Ra and Ra activity concentration, however the

system did have its advantages and disadvantages. One obvious advantage was

the instantaneous radioactivity information that could be obtained in the field,

without having to transport radioactive samples for hundreds of kilometres back

to the laboratory. Another advantage was the relatively short acquisition time

for readings, due to the high efficiency of the scintillating NaI(Tl) 2¼” crystal

(600 s) compared to the semi-conductor HPGe crystal (60,000 s). However,

including the Pb shield, the system weighed approximately 30 kg, which was a

100
significant disadvantage. In addition, the system had a lower energy resolution

compared to the HPGe detectors.

As a result of the findings presented in this work, it was found that whilst

sludge farming was useful in eliminating harmful hydrocarbons from the sludge,

it still comes up short in the reduction of radioactivity concentrations down to

ambient soil levels. For example, although dilution factors of up to 5 times were

used, in an effort to reduce the activity concentration of 226Ra, the treated strips

still showed activity concentrations up to ten times higher than the ambient

levels found at both Nimr and Marmul sludge farms. Despite the daily tilling of

the treated sludge, some hotspots > 1 kBq kg-1 also remained on the strips.

More specifically, this study found that sludge activity concentrations from

Bahja, Nimr and Marmul sludge farms ranged from 0.03-3.69, 0.01-6.04,

0.01-5.16 and 0.05-0.95 kBq kg-1 for 226

Ra, 228
Ra, 228
Th and 40
K, respectively.
226
In addition, 25% and 10% of the untreated sludge piles had Ra activity

concentration exceeding 1 kBq kg-1, at Bahja and Marmul farms, respectively.

226
Bahja sludge farm had the highest mean Ra activity concentration of

3289 Bq kg-1, while Nimr and Marmul sludge farms had similar 226
Ra mean

activity concentrations of 343 and 356 Bq kg-1, respectively. Nimr and Marmul

mean activity concentrations were found to be lower than the mean activity

concentrations for Bahja sludge piles, by one order of magnitude. Similarly, the

Bahja sludge was found to be the oldest, with a mean age of 9.0 ± 0.4 years,

while the Nimr and Marmul sludge had similar ages of 4.2 ± 0.3 and

3.6 ± 0.4 years, respectively. The nascent Nimr sludge radioactivity results can

101
now be used as a baseline with which to compare future nascent oil sludge

originating from Nimr station. They can also be used as a reference point when

formulating trends in relation to the different types of new technologies that

may be used in the oil recovery process.

This study also found that the average radium isotope activity concentration

in Oman oil scales fell within the lower end of the range of activity

concentrations reported elsewhere (0.1-15,000 kBq kg-1). The range of 226

Ra

and 228Ra were 3.38-17.30 and 1.36-4.31 kBq kg-1, respectively. The mean 226Ra

activity concentration of oil scales (8.940 kBq kg-1) was also found to be higher

than the mean activity concentration of the farm sludge found in Bahja, Nimr

and Marmul, which were 3.289, 0.343 and 0.356 kBq kg-1, respectively.

210
Both oil and gas scales contained detectable levels of Pb, however only

the gas scales were characterised by the presence of high activity concentrations
210 210
of Pb. In gas scales, the activity concentration of Pb ranged from

0.959-66.405 kBq kg-1, while the corresponding range for the oil scales was

3.06-7.59 kBq kg-1. Oil and gas scales, and barrel stored sludge also contained
227
Ac, with maximum activity concentrations of 123 ± 17, 181 ± 4 and 641

± 66 Bq kg-1, respectively. As such, care should be taken when clearing these

scales from oil and gas pipes, particularly in terms of exposure pathways that

involve direct irradiation, inhalation and ingestion.

Many petroleum companies in Oman dispose of excess produced water in

evaporation in ponds, or by pumping it into producing reservoirs, and

102
 227
abandoned deep and shallow wells. As outlined above, during this study, Ac

was detected for the first time in oil scales and sludge, however it was not

detected in produced water evaporation pond sediments, because it is most

likely transported as a vector and deposited with scale before reaching the
238 232
ponds. However, U and Th progeny along with 40K were detected in the
226
Al-Noor evaporation pond sediment with activity concentrations for Ra,
228 228 40
Ra, Th and K ranging from 0.107-3.260, 0.010-0.583, 0.005-0.205 and

0.030-0.837 kBq kg-1, respectively. These activity concentrations are similar to

the activity concentrations of untreated sludge piles found in Bahja, Nimr and

Marmul. Hence, this work established that pond sediment is also contaminated

by enhanced NORM and caution should be exercised during its disposal.

In conclusion, this study provided the first ever information on the

radioactivity concentration of treated and untreated sludge, oil and gas scales,

barrel stored sludge and evaporation pond sediment for oilfields in the Southern

Oman Directorate. The information provided in this chapter may be used as

reference for NORM activity concentration assessments in the Oman oil

industry and it may also be used as a baseline for possible future assessments in

both the onshore and offshore oil rigs of the Northern Oman Directorate.

Finally, this pioneering study is also important since similar data is yet to be

published for neighbouring oil producing Gulf countries.

103
104
Chapter 5 GAMMA DOSE RATES AT SLUDGE
FARMS IN OILFIELDS OF THE
SOUTHERN OMAN DIRECTORATE

5.1 Introduction

This chapter presents findings in relation to gamma dose rates measured in

the air at and around sludge farms in the southern Oman Directorate. The

chapter begins with a brief outline of the terrestrial and cosmic components of

gamma dose in the air, followed by an overview of gamma dose rates in the

petroleum industry. It then goes on to present gamma dose rates for the sludge

farms, over both untreated sludge piles and treated sludge strips (refer to

Chapter 4, Section 4.2.1 for details of the sludge farming process), as well as the

gamma dose rate correlations with the main radionuclides present in the sludge,

namely 226Ra, 228Ra and 40K.

5.2 Terrestrial and cosmic gamma dose rates

Gamma dose rates in the air, from both cosmic and terrestrial sources, have

been the focus of a large number of international studies over the last four

decades, with many factors found to affect the measured rate. The terrestrial

component of the gamma dose rate is dependent on the depth and lateral

distribution profile of activity concentrations of the primordial series 232Th, 238U

and 235U, and the primordial radionuclide 40K, along with soil type, composition

and moisture content. Measurements performed on Anthropomorphic phantoms,

in order to determine dose to organ, and effective dose, have shown that there is

105
a strong dependence of measured dose on radiation energy and incident angle

(Saito and Jacob, 1995). The cosmic component of the gamma dose rate, on the

other hand, is dependent on the altitude at which the measurements are carried

out. The worldwide outdoor altitude adjusted value for the cosmic component of

gamma dose rate is 460 µSv y-1, reported by UNSCEAR (2000).

A survey on outdoor terrestrial gamma radiation in the Sultanate of Oman,

conducted by Goddard (2002), reported that most of Oman’s surface rock is

limestone, which is low in primordial uranium and thorium. Hence, the average

gamma dose rate, measured at the conventional height of 1 m above the ground,

was lower than the world average of 0.45 mSv y-1, with the mean population

weighted dose rate for Oman found to be 0.30 mSv y-1. Goddard also tested the

validity of measured ambient dose rates, using both the ICRU (1995) and Saito

and Jacob’s (1995) dose coefficient models, on activity concentration of soil or

rock collected from the in situ measurement locations, and developed the

following equation, which gave a strong linear correlation (R2) of 0.84:

Dm = 0.89 Dc - 0.17 (5.1)

where Dm and Dc are the measured and predicted dose rates.

In addition to Goddard (2002), many other authors have also modelled

gamma dose rates based on activity concentrations that arise from natural

sources in the ground (Lovborg et al., 1979, Kocher and Sjoreen, 1985,

Battaglia and Bramati, 1988, Deworm et al., 1988, Chen, 1991, Clark et al.,

1993, Saito and Jacob, 1995, UNSCEAR, 2000, Losana et al., 2001, Ajayi,

2002). Carter and Sonter (2003) reviewed much of this literature and tabulated

106
 238
the conversion coefficients used in each study, to find dose rates from U,
232 40
Th and K activity concentrations. The conversion coefficients differed for

the three radionuclides and varied by a factor of about two, ranging from

0.28-0.52 µSv h-1 per Bq g-1 for 238

U, 0.295-0.73 for 232
Th, and 0.029-0.05 for
40
K.

Saito and Jacob (1995) also calculated Kerma coefficient factors at 1 m

height per disintegration for each individual radionuclide in the main primordial
40
series and K (see Table 5.1). These conversion factors allowed for the

calculation of air Kerma for individual radionuclides, which showed that 98% of
238 214
the U series air Kerma was due to only two radionuclides, being Pb and
214 232
Bi. Further calculations also showed that 90% of the Th series total air

Kerma was due to 228Ac and 208Tl. This finding indicates that, while the series is
226 228
in equilibrium, Ra and Ra, along with their precursors, only make a small

contribution to the total measured gamma dose rate.

107
Table 5.1: Air Kerma rate at 1 m height per disintegration rate (nGy h-1 per Bq kg-1) of the parent nuclide per unit soil weight for natural sources
uniformly distributed in the ground (adapted from Saito and Jacob)
238 232 235 40
U Kerma rate per unit Th Kerma rate per unit U Kerma rate per unit K Kerma rate per unit
series activity series activity series activity activity
(µGy h-1 per Bq g-1) (µGy h-1 per Bq g-1) (µGy h-1 per Bq g-1) (µGy h-1 per Bq g-1)
238 4.33x10-5 232 4.78x10-5 235 3.06x10-2 40 4.17x10-2
U Th U K
234 9.47x10-4 228 5.45x10-5 231 1.80x10-3
Th Ra Th
234
Pam 4.30x10-3 228
Ac 2.21x10-1 231
Pa 6.89x10-3
234 4.49x10-4 228 3.44x10-4 227 3.54x10-5
Pa Th Ac
234 5.14x10-5 224 2.14x10-3 227 2.10x10-2
U Ra Th
230 6.90x10-5 220 1.73x10-4 223 1.15x10-4
Th Rn Fr
226 1.25x10-3 212 2.77x10-2 223 2.39x10-2
Ra Pb Ra
222 8.78x10-5 212 2.72x10-2 219 1.25x10-2
Rn Bi Rn
214 5.46x10-2 208 3.26x10-1 215 5.11x10-5
Pb Tl Po
214 4.01x10-1 211 1.70x10-2
Bi Pb
210 1.51x10-4 211 1.08x10-2
Tl Bi
210 2.07x10-4 207 5.67x10-4
Pb Tl
Total 4.63x10-1 6.05x10-1 1.25x10-1 4.17x10-2

108
5.2.1 Gamma dose rates in the petroleum industry

In the petroleum industry, it is recommended that external gamma radiation

dose surveys on installations should be conducted both periodically and during

shutdowns. As discussed in Chapters 1 and 4, in addition to 40K and 227Ac (235U

210 226 238
series), it is mainly radium isotopes and Pb (one of Ra progeny – U
238 232
series) from the U and Th series, which are brought to the surface during

the oil extraction process. These radium isotopes and their progeny accumulate

on the internal walls of pipes and wellheads and the external radiation dose at
226
these sites is mainly from the gamma energies of Ra and its short-lived
214 214 208
daughters, primarily Pb and Bi. Higher energy photons of Tl (one of
228 232
Ra progeny – Th series) can also be encountered when the scale has

accumulated over a period of several months. Pb-210, on the other hand, has a

soft gamma of 46 keV, which cannot be detected outside the pipes by a

conventional dose rate meter. However this isotope is toxic if inhaled or

ingested in the form of dust particles, during plant maintenance.

Ac-227 was also detected in sludge, oil and gas scales, and this also

contributes to the radio-toxicity of these materials. Ac-227 has nine radioactive

227 223 219
progeny (refer to Chapter 1, Figure 1.2 (c)), with Th, Ra and Rn being

the main gamma emitting radionuclides. Ac-227 and its progeny are responsible
235
for 69% of U series air Kerma (Table 5.1). As outlined in Chapter 4,

Section 4.3.1.2 and Table 4.11 adapted from (ICRP68), the committed effective
227
dose coefficient from Ac, through the inhalation pathway, is 169, 360 and
226 210 228
208 times higher than that of Ra, Pb and its progeny, and Ra,

109
 227
respectively. Although the committed effective dose coefficient from Ac

through the ingestion pathway is in the same order of magnitude as those for
226
Ra, 210Pb and progeny, and 228Ra, its annual ingestion radioactivity limits are

80 and 10 times lower than those of 238U and 226Ra, respectively (ICRP, 1991).

As outlined in recently published literature (Paranhos Gazineu et al., 2005,

Salih et al., 2005), the type of duties given to temporary contract workers in the

petroleum industry is one area that requires significant attention. These duties

tend to include equipment maintenance, clearing radioactive sludge from

separation tanks, scale scraping and other general cleaning, which often pose

considerable risks from a radiation protection point of view. Whilst dose rates

outside closed vessels and pipes are usually less than 7.5 µSv h-1, dose rates as

high as 80 μSv h-1 have been reported, which can be attributed to radon

daughter deposits on the surface of some equipment (Kolb and Wojcik, 1985).

As reported by Hamlat et al. (2001), during wellhead maintenance and the

clearing of sludge from separation tanks, the dose rates can be much higher. For

example, the annual effective dose rates due to gamma radiation were found to

be 0.48, 0.04 and 0.6 mSv y-1, for normal activities in the oil sector, 1 m away

from the pipes and separation tanks, and in storage tanks and wellheads,

respectively. However, the dose rates inside these structures will be higher

again, by a factor of at least 5, depending on the extent and configuration of the

contamination. The annual effective dose received by such workers can

therefore be greater than 3 mSv y-1 (Smith, 1987).

110
 A comprehensive NORM survey of all PDO station equipment, manifolds,

wellheads and sludge farms is conducted by a scintillation count rate meter

(mini-900 meter coupled with an A44 scintillation probe) at least once every

four years (Petroleum Development Oman, 2005). During these surveys, a

NORM contaminated location is indicated by a reading of five CPS above the

background count rate of three CPS, and any facilities and equipment found to

be NORM contaminated are labelled and recorded, in order to alert PDO

personnel and contract workers to the risks (Petroleum Development Oman,

2005).

5.3 Materials and Methods

Gamma dose rates were measured directly from both untreated sludge piles

and treated sludge strips in Bahja, Nimr and Marmul sludge farms.

Measurements were carried out at a height of 1 m, using portable energy

compensated GM-tube, coupled with Mini-Instrument Type 6-80 (refer to

Chapter 3, Section 3.5 for meter calibration and measurement technique details).

The instrument was calibrated before and after the field measurements and the

readings were within a 10% error limit. Calibrations were conducted using a

certified Amersham gamma radiation source of 137Cs.

A total of 77 direct gamma dose rates were recorded, 34 of which were from

untreated sludge piles and 43 of which were from treated sludge strips. The
226 228
main radionuclides found in the sludge were Ra (T½: 1602 years), Ra (T½:

5.75 years) and their progeny, as well as 40K. Gamma dose rates were correlated

111
 226 228
with Ra, Ra and 40K activity concentrations, which were obtained by both

portable NaI(Tl) gamma spectroscopy and laboratory HPGe systems (refer to

Chapter 3, Sections 3.3 and 3.4). In-situ gamma spectroscopy measurements

were performed at the same locations as the gamma dose rate measurements,

and additional gamma dose rates were also derived from activity concentrations

using an empirical relation (equation 5.2 below).

5.4 Results and discussion

5.4.1 Correlation between measured and predicted gamma

dose rate

The cosmic ray component of 0.06 ± 0.01 µSv h-1 (equivalent to 530

± 90 µSv y-1) derived by this study was reasonably close to the worldwide

outdoor, altitude adjusted value of 460 µSv y-1 (UNSCEAR, 2000). A study

conducted by Bouville and Lowder (1988) on global cosmic radiation,

calculated the collective dose equivalent for the world’s population as a function

of altitude and geographic latitude, in various large cities around the world.

Pakistan was the closest country to Oman that was included in the above study,

and it had an annual dose equivalent of 430 µSv, which is also close to the

empirically derived value obtained in this study (530 ± 90 µSv y-1).

Measured and predicted gamma dose rates using conversion factors

published by UNSCEAR (2000) were also compared, as illustrated in

Figure 5.1. On average, the gamma dose rates were overestimated by 64% using

UNSCEAR (2000) formula, however, there was a strong linear correlation

coefficient (R2) of 0.95 between measured and predicted gamma dose rates.

112
 1.2
Measured gamma dose rate (µSv h-1)

1.0

0.8

0.6

0.4

0.2

0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0

Predicted gamma dose rate (µSv h-1)

Figure 5.1: Relation between measured and predicted gamma dose rates using
UNSCEAR (2000) dose conversion factors.

5.4.2 Development of a new gamma dose rate empirical model

In order to find more accurate dose coefficients, a new correlation between

226 228 40
Ra, Ra and K activity concentrations and gamma dose rate was defined

by multiple regressions using the SigmaPlot (Version 10.0) program. The

program utilises the Marquardt-Levenberg Algorithm to find the coefficients of

the independent variables that give the best fit between the equation and the

data. This resulted in the development of the following empirical relation, which

includes uncertainties and gave a correlation coefficient (R2) of 0.95. This

equation was used to determine the effective gamma dose rate for petroleum
226 228 40
treated and untreated sludge, as a result of Ra, Ra and K activity

concentrations:

113
H• = (0.178 ± 0.007) CRa-226 + (0.230 ± 0.038) CRa-228 + (0.016 ± 0.046) CK-40 + HCosmic

(5.2)

where H• is the effective dose rate in µSv h-1, CRa-226, CRa-228 and CK-40 are the
226 228 40
activity concentrations of Ra, Ra and K in Bq g-1, respectively, and

HCosmic is the cosmic component of gamma dose rate, which was equal to 0.06

± 0.01 µSv h-1.

The corresponding UNSCEAR (2000) relationship used to generate

Figure 5.1 was:

H• = (0.462) CU-238 + (0.604) CTh-232 + (0.0417) CK-40 (5.3)

where H• is the effective dose rate in µSv h-1, and CU-238, CTh-232 and CK-40 are

the activity concentrations of 226Ra, 228Ra and 40K in Bq g-1 respectively.

The empirical relationship developed in this study generated approximately

226 228
30% variation between Ra and Ra dose conversion coefficients, which
238
compared well to the UNSCEAR (2000) U:232Th coefficient ratio, as well as

the total air Kerma ratio of 238U and 232Th presented in Table 5.1. However, the

calculated dose conversion coefficients were lower than the range found in

literature and 60% lower than dose coefficients reported by UNSCEAR (2000),

which may be due to one or a combination of the following reasons:

• The ambient soil radionuclides exist in unperturbed soil, whereas the

sludge piles are in a perturbed form, where the newly dumped, less

compacted sludge soil density may be lower than the ambient soil

density;

114
 • The presence of heavy metal sediments and corrosive particles in the

petroleum sludge (APPEA, 2002, Omar et al., 2004) may lead to a

greater gamma attenuation coefficient relative to ambient soil;

• The ambient soil measurements were usually taken from flat extended

land, whereas untreated sludge piles are pyramidal, with a height of

1.75 ± 0.25 m and a base area of 4.0 ± 0.5 m2, and the measurements

were taken from the top of the piles. Similarly, the treated sludge strips

were laid over compacted land and had an average height of 0.4 ± 0.1 m.

The strips are 6 ± 2 m in width and 75 ± 10 m in length, separated by

4-8 m of open space, and measurements were usually taken near the

centre of the strips;

• Ambient soil radionuclides are usually found with the complete

primordial series existing in secular equilibrium (ignoring radon isotopes

exhalation) with the parent radionuclide, whereas the petroleum sludge

natural series starts from radium isotopes and not all radionuclides may

have reached equilibrium at the time of measurement; and

232
• There is a transient rather than secular equilibrium in the Th decay

chain between 228Ra and 228Th.

The empirical relation also resulted in a strong correlation between

measured and predicted gamma dose rates, as illustrated in Figure 5.2, with a

linear correlation coefficient (R2) of 0.96 and a correlation equation of:

H•Measured = (1 ± 0.025) H•Predicted + (0 ± 0.009) (5.4)

where H•Measured is the measured effective gamma dose rate, and H•Predicted is the
predicted or synthesised effective gamma dose rate.

115
 1.2

Measured gamma dose rate (µSv h-1)

1

0.8

0.6

0.4

0.2

0
0.0 0.2 0.4 0.6 0.8 1.0 1.2

Predicted gamma dose rate (µSv h-1)

Figure 5.2: Relation between measured and empirically determined gamma dose
rates.

Dose coefficients for the ambient soil measurements conducted during this

study were higher than those found for untreated and treated sludge

(equation 5.2 above). In fact, the calculated dose coefficients were close to the

coefficients reported by UNSCEAR (2000). Using multiple regression, the

below equation 5.5 was derived for the ambient soil samples taken from the

Southern Oman Directorate, which gave a correlation coefficient (R2) of 0.66.

However, the coefficient uncertainties were relatively high, which is likely a

result of the small number of available readings:

H• = (0.455) CRa-226 + (0.595) CRa-228 + (0.041) CK-40 + HCosmic (5.5)

where the symbols carry the same meaning as those in equation 5.2.

116
 Separating the untreated from the treated sludge farm data produced

somewhat different dose coefficients (see below), where the treated sludge dose

coefficients were about 20% higher than the untreated sludge values. However,

the values did overlap within the uncertainties:

H•Untreated = (0.178 ± 0.011) CRa-226 + (0.232 ± 0.057) CRa-228 + (0.016 ± 0.076) CK-40
+ HCosmic
(5.6)

H•Treated = (0.217 ± 0.031) CRa-226 + (0.283 ± 0.048) CRa-228 + (0.020 ± 0.019) CK-40
+ HCosmic
(5.7)

This finding supports the five prior assumptions about untreated pile

geometry, soil constituent and density differences. Since the treated sludge

strips were a mixture of petroleum sludge and ambient soil, and were laid on flat

land, their derived dose coefficients were higher than untreated sludge values.

This is important when explaining the low dose coefficients that were obtained

for untreated sludge, and demonstrates that reported literature values for soil

radioactivity and gamma radiation dose do not strictly apply to petroleum

industry sludge piles.

5.4.3 Gamma dose rate measurements

During this field work, the highest measured gamma dose rate was recorded

at Bahja NORM store yard, from the sludge stored in barrels, where the

maximum barrel surface reading was 40 µSv h-1. These barrels contained
226
petroleum sludge with Ra activity concentrations as high as 223 kBq kg-1

(refer to Chapter 4, Section 4.3.4 for radioactivity in the sludge stored in

117
barrels). As expected, dose rates increased with radionuclide activity

concentrations of 226Ra and 228Ra and their progeny.

Goddard (2002) surveyed natural radioactivity in eight governorates of the

Sultanate of Oman, namely Muscat, Sharqiyah, Batinah, Dakhliyah, Wusta

(where this work was conducted), Dhahirah, Dhofar and Musandam. The mean

national average gamma dose rate from terrestrial gamma sources was

33.2 nGy h-1 and using a conversion factor between absorbed dose in air and

effective dose of 0.86 Sv Gy-1 (Clark et al., 1993), the national average effective

gamma dose rate becomes 28.6 nSv h-1. Specific to the Al-Wusta region, where

Al-Noor, Bahja, Nimr and Marmul were situated, the gamma dose rate due to

terrestrial sources was 33.6 ± 5.0 nGy h-1 (n = 72), within a range of

19.4-102.4 nGy h-1 (Goddard, 2002). Using the same conversion factor as

above, this translates to an effective gamma dose rate of 28.9 ± 4.3 nSv h-1. Our

measured Al-Noor, Bahja, Nimr and Marmul average ambient soil effective

gamma dose rate value, excluding the cosmic component of 60 ± 11 nSv h-1,

was 25.5 ± 13.8 nSv h-1, which is close to Goddard’s average value for the

region.

A total of 77 measured gamma dose rates from untreated sludge piles and

treated sludge strips are presented in Tables 5.2 and 5.3, respectively, along with

their sample identification, geographical location, gamma dose rate and the
226 228 40
corresponding Ra, Ra and K activity concentrations. A summary of the

gamma dose rates for both untreated and treated sludge at the three farms

(excluding hotspots in Marmul’s treated sludge strip numbers 7 and 44) is also

given in Table 5.4. The maximum gamma dose rates for the untreated sludge

118
piles at Bahja, Nimr and Marmul were 1.116, 0.238 and 0.613 µSv h-1,

respectively. The mean values for the three locations were 0.667 ± 0.209, 0.169

± 0.033 and 0.101 ± 0.207 µSv h-1, respectively. The values were all above the

natural background value of 0.086 ± 0.014 µSv h-1 and Bahja had the highest
226 228
gamma dose rates, due to the relatively higher Ra and Ra activity

concentrations, with ranges of 1-5 and 0.1-0.5 kBq kg-1, respectively.

119
Table 5.2: Measured gamma dose rates and 226Ra, 228Ra and 40K activity concentrations for Bahja, Nimr and Marmul untreated sludge piles
226 228 40
Sample ID Location 40QUTM Gamma dose rate Ra Ra K
Easting Northing (µSv h-1) (Bq kg-1) (Bq kg-1) (Bq kg-1)
Bahja
G01 0398306 2198873 0.496 ± 0.007 2210 ± 40 191 ± 7 185 ± 21
G02 0398318 2198877 0.464 ± 0.007 1310 ± 20 103 ± 5 252 ± 15
G03 0398316 2198885 0.591 ± 0.008 2980 ± 30 203 ± 6 229 ± 18
G04 0398318 2198888 0.530 ± 0.007 2150 ± 70 143 ± 11 264 ± 27
G05 0398318 2198898 0.596 ± 0.008 2240 ± 40 150 ± 5 254 ± 21
G06 0398328 2198909 1.116 ± 0.010 4520 ± 50 200 ± 10 209 ± 23
G07 0398363 2198960 0.550 ± 0.007 4000 ± 40 253 ± 9 217 ± 23
G14 0398367 2198958 0.440 ± 0.007 1955 ± 56 172 ± 14 524 ± 122
G15 0398360 2198953 0.637 ± 0.008 2981 ± 69 289 ± 18 597 ± 150
G16 0398355 2198950 0.686 ± 0.008 3221 ± 71 271 ± 18 566 ± 153
G17 0398351 2198944 0.740 ± 0.008 3799 ± 77 315 ± 19 591 ± 165
G18 0398342 2198933 0.851 ± 0.009 3875 ± 79 375 ± 21 779 ± 171
G19 0398340 2198929 0.949 ± 0.010 4336 ± 82 366 ± 21 767 ± 178
G20 0398333 2198920 1.098 ± 0.010 4934 ± 89 472 ± 23 758 ± 190
G21 0398330 2198915 0.693 ± 0.008 2908 ± 68 258 ± 17 638 ± 147
G22 0398320 2198906 0.744 ± 0.009 3445 ± 73 287 ± 18 954 ± 162
G23 0398310 2198896 0.591 ± 0.008 2444 ± 63 268 ± 18 742 ± 140
G24 0398309 2198890 0.529 ± 0.007 2274 ± 60 200 ± 15 409 ± 129
G25 0398300 2198878 0.378 ± 0.006 1651 ± 53 198 ± 15 469 ± 115

120
Table 5.2 (Continued): Measured gamma dose rates and 226Ra, 228Ra and 40K activity concentrations for Bahja, Nimr and Marmul untreated sludge
piles
226 228 40
Sample ID Location 40QUTM Gamma dose rate Ra Ra K
Easting Northing (µSv h-1) (Bq kg-1) (Bq kg-1) (Bq kg-1)
Nimr
N01 0383329 2051550 0.156 ± 0.004 531 ± 13 139 ± 3 446 ± 10
N02 0383337 2051562 0.151 ± 0.004 403 ± 17 138 ± 5 487 ± 14
N03 0383356 2051569 0.159 ± 0.004 291 ± 14 118 ± 3 405 ± 10
N04 0383353 2051598 0.177 ± 0.004 314 ± 10 114 ± 3 457 ± 9
N05 0383309 2051584 0.166 ± 0.004 320 ± 11 123 ± 2 457 ± 9
N06 0383296 2051560 0.134 ± 0.004 285 ± 10 95 ± 3 439 ± 9
N07 0383347 2051609 0.238 ± 0.005 639 ± 17 270 ± 4 134 ± 10

Marmul
M01 0319390 2014275 0.150 ± 0.004 195 ± 20 83 ± 12 47 ± 43
M02 0319393 2014288 0.076 ± 0.003 36 ± 6 9±1 119 ± 6
M03 0319385 2014287 0.079 ± 0.003 42 ± 4 10 ± 1 135 ± 5
M04 0319378 2014292 0.076 ± 0.003 36 ± 4 7±1 118 ± 5
M05 0319370 2014292 0.077 ± 0.003 38 ± 4 9±1 103 ± 5
M06 0319365 2014314 0.123 ± 0.003 125 ± 9 92 ± 3 639 ± 11
M08 0319385 2014271 0.613 ± 0.008 918 ± 21 845 ± 7 548 ± 15
M09 0319392 2014271 0.448 ± 0.007 1022 ± 24 1557 ± 7 359 ± 16
Maximum 1.116 4934 1557 954
Minimum 0.076 36 7 47
Median 0.480 1803 195 443
Mean (standard deviation) 0.456 (0.303) 1836 (1557) 245 (281) 421 (234)
Number 34

121
Table 5.3: Measured gamma dose rates and 226Ra, 228Ra and 40K activity concentrations for Bahja, Nimr and Marmul treated sludge strips
226 228 40
Sample ID Location 40QUTM Gamma dose rate Ra Ra K
Easting Northing (µSv h-1) (Bq kg-1) (Bq kg-1) (Bq kg-1)
Bahja
Strip # 018 0398766 2198993 0.081 ± 0.003 51 ± 10 13 ± 10 159 ± 30
Strip # 030 0398675 2198899 0.083 ± 0.003 55 ± 10 13 ± 10 175 ± 32
Strip # 043 0398775 2198963 0.085 ± 0.003 68 ± 10 8±7 175 ± 32
Strip # 065 0398736 2198925 0.083 ± 0.003 58 ± 10 11 ± 9 163 ± 31
Strip # 070 0398698 2198876 0.084 ± 0.003 71 ± 11 13 ± 10 107 ± 29
Strip # 073 0398682 2198837 0.085 ± 0.003 52 ± 10 17 ± 12 191 ± 33
Strip # 076 0398659 2198802 0.076 ± 0.003 37 ± 9 15 ± 11 178 ± 30
Strip # 078 0398637 2198780 0.082 ± 0.003 62 ± 10 11 ± 9 172 ± 32
Strip # 080 0398617 2198763 0.086 ± 0.003 63 ± 10 11 ± 9 198 ± 33

Nimr
Strip # 029 0383548 2051927 0.072 ± 0.003 18 ± 9 22 ± 8 82 ± 24
Strip # 039 0383612 2051829 0.074 ± 0.003 56 ± 11 19 ± 7 75 ± 27
Strip # 044 0383648 2051790 0.077 ± 0.003 22 ± 10 26 ± 9 102 ± 27
Strip # 052 0383579 2051742 0.080 ± 0.003 34 ± 10 20 ± 8 109 ± 27
Strip # 085 0383370 2052107 0.077 ± 0.003 49 ± 10 12 ± 6 84 ± 26
Strip # 100 0383387 2051795 0.078 ± 0.003 36 ± 8 8±4 184 ± 30
Strip # 111 0383498 2051667 0.094 ± 0.003 85 ± 13 29 ± 10 126 ± 34
Strip # 116 0383401 2051590 0.083 ± 0.003 46 ± 9 12 ± 6 137 ± 29
Strip # 119 0383375 2051622 0.076 ± 0.003 37 ± 5 10 ± 1 118 ± 6
Strip # 126 0383332 2051726 0.075 ± 0.003 17 ± 9 23 ± 8 132 ± 27
Strip # 143 0383291 2051664 0.078 ± 0.003 32 ± 8 12 ± 6 113 ± 26

122
Table 5.3 (Continued): Measured gamma dose rates and 226Ra, 228Ra and 40K activity concentrations for Bahja, Nimr and Marmul treated sludge
strips
226 228 40
Sample ID Location 40QUTM Gamma dose rate Ra Ra K
Easting Northing (µSv h-1) (Bq kg-1) (Bq kg-1) (Bq kg-1)
Marmul
Strip # 005 0319306 2014175 0.078 ± 0.003 38 ± 10 16 ± 6 119 ± 28
Strip # 007 h 0319248 2014072 0.327 ± 0.006 1920 ± 54 190 ± 30 300 ± 116
Strip # 011 0319230 2014186 0.076 ± 0.003 66 ± 12 17 ± 7 54 ± 27
Strip # 013 0319161 2014080 0.078 ± 0.003 63 ± 11 13 ± 6 114 ± 30
Strip # 018 0319120 2014219 0.086 ± 0.003 62 ± 12 25 ± 8 39 ± 27
Strip # 021 0319058 2014135 0.081 ± 0.003 56 ± 11 19 ± 7 58 ± 27
Strip # 024 0319079 2014233 0.081 ± 0.003 52 ± 12 24 ± 8 53 ± 27
Strip # 025a 0319352 2014140 0.101 ± 0.003 153 ± 17 28 ± 9 141 ± 40
Strip # 025b 0319352 2014140 0.108 ± 0.003 181 ± 16 9±5 240 ± 44
Strip # 044 h - - 0.362 ± 0.006 2080 ± 40 184 ± 5 136 ± 15
Strip # 069 0319026 2014173 0.091 ± 0.003 80 ± 12 15 ± 6 284 ± 39
Strip # 102a 0319037 2014148 0.095 ± 0.003 67 ± 15 51 ± 14 214 ± 40
Strip # 102b 0319042 2014179 0.105 ± 0.003 92 ± 20 100 ± 22 204 ± 47
Strip # 102c 0319046 2014183 0.114 ± 0.003 180 ± 24 130 ± 27 137 ± 53
Strip # 112 0319143 2014210 0.077 ± 0.003 56 ± 11 21 ± 8 35 ± 26
Strip # 115 0319174 2014200 0.079 ± 0.003 22 ± 10 23 ± 8 166 ± 30
Strip # 118 0319202 2014078 0.084 ± 0.003 59 ± 11 15 ± 6 110 ± 29
Strip # 148 0319125 2014094 0.079 ± 0.003 27 ± 11 31 ± 10 103 ± 29
Strip # 183 0319261 2014182 0.081 ± 0.003 37 ± 12 31 ± 10 54 ± 27
Strip # 186 0319091 2014110 0.078 ± 0.003 42 ± 9 12 ± 5 79 ± 25
Strip # 189 0319199 2014192 0.079 ± 0.003 44 ± 10 15 ± 6 93 ± 27
Strip # 192 0319318 2014095 0.106 ± 0.003 118 ± 13 5±3 205 ± 38
Strip # 193 0319283 2014108 0.099 ± 0.003 121 ± 14 11 ± 5 197 ± 38

123
Table 5.3 (Continued): Measured gamma dose rates and 226Ra, 228Ra and 40K activity concentrations for Bahja, Nimr and Marmul treated sludge
strips
226 228 40
Sample ID Location 40QUTM Gamma dose rate Ra Ra K
Easting Northing (µSv h-1) (Bq kg-1) (Bq kg-1) (Bq kg-1)
Maximum 0.114 181 130 284
Minimum 0.072 17 5 35
Median 0.081 56 15 126
Mean (standard deviation) 0.085 (0.010) 63 (39) 22 (23) 134 (58)
Number 43
h: hotspots measured on treated sludge strips, not included in the final statistical calculations

124
Table 5.4: Summary of field measured gamma dose rates (µSv h-1) at 1 m height
for Bahja, Nimr and Marmul petroleum sludge treatment farms’
Bahja Nimr Marmul
Untreated Treated Untreated Treated Untreated Treated

piles strips piles strips piles strips

Maximum 1.116 0.086 0.238 0.094 0.613 0.114

Minimum 0.378 0.076 0.134 0.072 0.076 0.076
Median 0.596 0.083 0.159 0.077 0.205 0.081
Mean 0.667 0.083 0.169 0.079 0.101 0.089
S.D. * 0.209 0.003 0.033 0.006 0.207 0.011
n# 19 9 7 11 8 19
* is the standard deviation
# is the number of readings

The maximum recorded gamma dose rates for treated sludge strips at Bahja,

Nimr and Marmul (excluding Marmul’s hotspots on treated sludge strips 7 and

44) were 0.086, 0.094 and 0.114 µSv h-1, respectively, while the mean gamma

dose rates were 0.083 ± 0.003, 0.079 ± 0.006 and 0.089 ± 0.011 µSv h-1,

respectively. The average values for the treated sludge strips were within the

average range of measured ambient soil gamma dose rates, being 0.086

± 0.014 µSv h-1. The treated sludge hotspot readings for strips 7 and 44 at

Marmul were 0.327 ± 0.006 and 0.362 ± 0.006 µSv h-1, respectively. The direct
226 228
correlation between gamma dose rate and both Ra and Ra activity

concentrations are shown in Figure 5.3.

125
 1.2
vh )
-1

1.0
rate (µS

500
0.8
400
mma dose

0.6

)
kg -1
300
0.4

(Bq
0.2 200
Ga

Ra
0.0

228
100
1000
2000
3000
226 4000 0
Ra (Bq 5000
kg -1)

Bahja untreated piles

Bahja treated strips
Nimr untreated piles
Nimr treated strips
Marmul untreated piles
Marmul treated strips

Figure 5.3: 3D graph of gamma dose rate relation with both 226Ra and 228Ra
activity concentrations.

126
 Although a strong correlation was observed between the measured gamma
226 228
dose rate and Ra and Ra, the correlation with 40K was only moderate. The

average measured gamma dose rate for untreated sludge in the Southern Oman

Directorate sludge farms was 0.456 ± 0.303 µSv h-1, while the average

measured gamma dose rate for treated sludge (excluding hotspots) was 0.085

± 0.010 µSv h-1. This difference in values was due to the sludge farming process

used at the farms, and that only sludge with activity concentrations < 1 kBq kg-1

was approved for the farming process. The average gamma dose rate for the

treated sludge was within the average range of measured ambient soil dose rate,

being 0.086 ± 0.014 µSv h-1.

5.4.4 Combining synthesised and measured gamma dose

rates
Using the mathematical model developed in this study, it was possible to

derive gamma dose rates for locations which only had activity concentration

data recorded. This produced additional 36 data points for gamma dose rates in

the oilfields of the Southern Oman Directorate. A box plot of the entire gamma

dose rate data is shown in Figure 5.4, where the total number of samples for

each location is reported beneath each box. The box plot shows that Bahja,

Nimr and Marmul untreated sludge piles have different gamma dose rate

profiles, however the gamma dose rates of the three treated sludge farm strips

are not significantly different. The location, number of samples, mean, median

and dose rate ranges are also summarised in Table 5.5.

127
 1.8
Above 90th percentile
90th percentile
75th percentile
1.5 Mean
Median
25th percentile
10th percentile
Gamma dose rate (µSv h-1)

1.2 Below 10th percentile

0.9

0.6

0.3

n = 23 n = 12 n = 14 n = 17 n = 16 n = 31
0.0
Marmul piles
Nimr piles
Bahja strips

Marmul strips
Bahja piles

Nimr strips

Location

Figure 5.4: Measured and predicted gamma dose rate profiles at a 1 m height for
untreated sludge piles and treated strips at Bahja, Nimr and Marmul sludge farms
(where n denotes the total number of samples at each location).

128
Table 5.5: Number of samples, mean, median and range of the dose rates for
untreated and treated sludge at Bahja, Nimr and Marmul obtained by both direct
measurement and empirical relation
Location Number Mean dose Median dose Dose rate
of rate rate range
samples (µSv h-1) (µSv h-1) (µSv h-1)
Bahja piles 23 0.702 ± 0.250 0.637 0.281 - 1.116
Nimr piles 14 0.166 ± 0.026 0.166 0.126 – 0.238
Marmul piles 16 0.345 ± 0.454 0.146 0.072 – 1.781
Bahja strips 12 0.084 ± 0.004 0.084 0.076 – 0.091
Nimr strips 17 0.109 ± 0.084 0.080 0.072 – 0.426
Marmul strips 31 0.115 ± 0.068 0.091 0.063 – 0.362
Total 113

Since no other published data was found on gamma dose rates in petroleum

sludge treatment farms, we could not make any comparisons with our

measurements and our empirically derived equations for dose coefficients. The

only related scientific literature found was by Smith et al. (1998), who

developed a theoretical model to find absorbed dose rates over a period of time

(up to 1000 years), using RESRAD computer code version 5.782, in order to

assess different scenarios of sludge farm remediated land, including residential,

agricultural, industrial and recreational use. For a 226Ra activity concentration of

185 Bq kg-1 above background, the expected dose was 0.6 mSv y-1, while the

empirical relationship for rehabilitated land derived through the experimental

work of this study (equation 5.7) gives a dose of 0.4 mSv y-1 for the same

activity concentration of 226Ra.

129
5.5 Conclusions

This work derived a new empirical relation between petroleum sludge

activity concentration and gamma dose rates at a height of 1 m above ground.

The derived conversion coefficients were at the lower end of the range found in

literature, for normal soils, which may have been caused by one or a

combination of the following factors: (1) the presence of heavy metal sediments

and corrosive particles in the petroleum sludge, leading to a greater attenuation

coefficient; (2) the radionuclides may not have reached equilibrium at the time

of measurement; (3) the ambient soil measurements are usually conducted on

flat extended land, whereas untreated sludge piles are in small heaps; and (4) the

greater soil density of ambient soil compared to less compacted untreated and

treated sludge. This resulted in a new empirical relation being developed for

petroleum sludge, in order to determine effective gamma dose rate from

radionuclide activity concentrations.

A strong correlation was observed between the measured gamma dose rate
226 228
and Ra and Ra, however the correlation with 40K was only moderate. The

average measured gamma dose rate for untreated sludge in the Southern Oman

Directorate sludge farms was 0.456 ± 0.303 µSv h-1, while the average

measured gamma dose rate for treated sludge (excluding hotspots) was 0.085

± 0.010 µSv h-1. This difference in values was due to the sludge farming process

used at the farms, in that only sludge with activity concentrations < 1 kBq kg-1

was approved for the farming process. The average dose rate for the treated

sludge was within the average range of measured ambient soil gamma dose rate,

being 0.086 ± 0.014 µSv h-1.

130
 The effective reduction of petroleum sludge gamma dose rates down to

ambient soil levels, using the sludge farming process, was clearly evidenced by

the results obtained in this study. However, hotspots were still present, which

still raise concern, considering that the desert terrain of mainly limestone

surface rock naturally contains only low concentrations of radionuclides. As

such, this study contributes important and significant knowledge on gamma

dose rates and the derivation of dose coefficients in the petroleum industry,

since no similar work has been reported to date.

131
132
Chapter 6 RADON-222 EXHALATION FROM
PETROLEUM INDUSTRY SCALE,
SLUDGE AND SEDIMENT

6.1 Introduction

Radon is a naturally occurring, highly mobile, chemically inert radioactive

222 238
gas. Its isotope Rn is part of the U series, produced by the radioactive
226
decay of Ra. Because radium is widely distributed in the earth’s crust, radon

is widely distributed too, with reports of radon detection in dwellings

throughout the world (UNSCEAR, 2001). Once formed by the radioactive decay
226
of Ra, it migrates freely as a gas or is dissolved in water, without being

trapped or removed by chemical reactions.

Whilst radon is inhaled on a regular basis by people all over the world, its

inert characteristics mean that it doesn’t interact with the respiratory system

lining, and a large proportion of the inhaled radon is usually exhaled. However,

the remaining inhaled portion, along with any ingested radon, does pose a

radiological risk from internal exposure of organs, because once inhaled or

ingested, radon and its short-lived progeny will deposit their entire alpha

particle energy in an immediate localised area. From the radiological hazard

220
point of view, Rn (224Ra progeny) does not pose as high a risk as that posed

by 222Rn, since 220Rn only has a few short-lived progeny, whereas 222Rn has two
210 210
long-lived progeny, Pb and Po, with half-lives of 22.3 years and
238
138.4 days, respectively (refer to Figure 1.2 in Chapter 1, Section 1.3 for U

and 232Th primordial radioactive decay series).

133
 Radon has long been known as one of the causes of lung cancer and the

radiological dangers of 222Rn reside in its four short-lived radioisotope progeny,

which can attach to ambient aerosols and be inhaled into the bronchial system.
222
Two of the Rn progeny (218Po and 214
Po) are alpha emitters with energies of

6.00 MeV and 7.69 MeV respectively. The other two (214Pb and 214Bi) are beta-

gamma emitters, which also contribute to the radiation dose (Wilson and Scott,
222
1993). On average, Rn is the highest single contributor to the ambient

radiation dose to the global human population, with inhalation exposure dose

from radon and its progeny estimated to be 1.2 mSv y-1 of the total of

2.4 mSv y-1 (UNSCEAR, 2000). The other contributors are external terrestrial

radiation, cosmic and cosmogenic, and ingestion exposure.

Due to its gaseous nature, radon can also be exhaled from the ground, as

well as from various building materials, and being chemically inert, it does not

react with other elements, as it finds its way to the atmosphere. The mechanism

of radon generation and transport, along with factors contributing to its

emanation from mineral grains, have been studied by many authors, e.g. Tanner

(1964, , 1980) Semkow (1990), Morawska and Phillips (1992), Greeman and

Rose (1996), Gomez Escobar et al. (1999), and Holdsworth and Akber (2004),

and generally involves processes such as emanation, diffusion, convection,

absorption (in the liquid phase) and adsorption (onto solid surfaces)

(UNSCEAR, 2000).

134
 The rate at which radon exhales from a material depends (along with other

factors) on the radon emanation fraction, which is the fraction of radon atoms

formed in a solid that escape and are free to migrate. This fraction varies

depending on several factors, but is largely determined by the physical

properties of the material bearing the radium nuclide. These include (i) radium

distribution within the material, (ii) porosity, (iii) granule surface area to volume

ratio, and (iv) the effective radon diffusion coefficient in the material. These

factors often interact in complex and counter-intuitive ways, such that the

process of radon emanation (and its consequent exhalation) tend to follow a

log-normal distribution (Rood et al., 1998, White and Rood, 2001).

Radon exhalation into the atmosphere is a two stage process – the first stage

involves emanation from the material into the porous space of the ground (as

described above), while in the second stage, the radon diffuses, either by a

process of molecular diffusion or by advection and/or convection for up to

several metres in the interstitial space, before emerging into the atmosphere.

The emergence of radon from the interstitial space to the atmosphere is termed

‘exhalation’.

As outlined in Chapter 4, Section 4.3.1.1, as oil is extracted from the

formation rock and brought to the surface, its temperature and/or pressure

decrease, which allows the solutes contained within the produced water to

precipitate. Consequently, during the extraction process, radium is co-

precipitated with barium, strontium and calcium, in the form of sulphates and

carbonates (Kolb and Wojcik, 1985, Jerez Vegueria et al., 2002a, Hamilton et

135
al., 2004, Al-Masri and Aba, 2005). This precipitation results in the formation

of hard and highly insoluble scale deposits on the interior walls of the tubular

and other production equipment. The 222Rn and 220Rn along with their progeny,

which exhaled from the scales, may also be present or build up in the crude oil

and gas streams (Rood et al., 1998, Worden et al., 2000). In addition to scale

formation, once the crude oil is transported from oil wells to processing stations,

oily sludge can form in separation tanks, as a result of the oil, water and gas

separation process. The precipitated oily sludge also contains enhanced

222 220
concentrations of radium isotopes and as a result, the exhaled Rn and Rn,

along with their progeny, may also be present and build up in the separation

tanks. However the separation tanks are ventilated prior to sludge clearing, in

order to remove H2S gas, which suggests that any radon accumulated in the

separation tank would also escape. Radon is also known to be soluble in both

organic matter and water, and therefore, the separated natural gas and produced

water streams would continue transporting radon isotopes even after the oil has
222
been extracted. The Rn long-lived decay product (210Pb) also forms a thin

radioactive film on the internal walls of gas pipes and vessels, with a reported

specific activity greater than 1 kBq g-1 (Hamlat et al., 2003a).

The earliest account of radon gas found in the hydrocarbon industry noted

its presence in Canadian natural gas, as reported by McLennan in 1904 (Satterly

and McLennan, 1918). Many authors have since investigated and published
222
reports on the presence of Rn in the natural gas industry. Whilst such

investigations are still ongoing, with the most recent work by authors including

Al-Masri and Shwiekani (2008) and Hamlat et al. (2003a), who evaluated

136
 222
activity flux and distribution of Rn and radiation exposure rates in the gas
222
industry, few have measured emanation factors of Rn from petroleum scales

e.g. White and Rood (2001) and Rood et al. (1998). In addition, this study is the
222
first ever to evaluate Rn exhalation rates from barrel stored oily sludge,

treated and untreated petroleum sludge and from sediments of a produced water
222
evaporation pond. This study also measured Rn exhalation rates from

petroleum scales and ambient soils, in order to make a preliminary assessment

222
of Rn exhalation from petroleum sludge samples, and then to compare

differences in both radon exhalation rates and radon exhalation to radium

concentration ratios for the different sample types.

6.2 Materials and methods

Overall, radon emanation rates were determined for 72 petroleum industry

samples and four ambient soil samples. A further six ambient soil locations

were assessed in Australia, for comparison. Field, as well as laboratory

measurements, were performed for six different sample types, including

ambient soils, petroleum scales, barrel stored oily sludge, treated sludge,

untreated sludge and evaporation pond sediments. The ambient soils were

collected from Al-Noor, Bahja, Nimr and Marmul (refer to map in Chapter 2,

Figure 2.1), while the petroleum scale and barrel stored oily sludge samples

were collected from Bahja NORM store yard. Treated and untreated sludge

samples were collected from Bahja, Nimr and Marmul sludge farms, and the

sediment samples were collected from the Al-Noor station produced water

evaporation pond. Grab sediment samples were collected using a metal scooper,

137
to a depth of about 5 cm, and placed in plastic bottles, along with a single bead

(up to 1 cm in diameter) and a single sand sample collected from barrels of an

unknown origin, that were stored in the Bahja NORM store yard. The reason for

collecting these two additional samples was because of their high gamma count

rate. The quantity of material collected for the entire set of samples varied from

100-300 g and all samples were then transported to the laboratory in Muscat for

radon emanation assessment and spectroscopy analysis. In order to preserve

their pore and grain structure, as well as the moisture and organic content, the

samples were not subjected to any vigorous preparation procedure before being

placed in the emanometer. A detailed outline of the materials and methods used

in this study can be found in Chapter 3, Section 3.6, which includes information
222
on the instruments used, as well as techniques applied for measuring Rn

exhalation rate.

6.3 Results and discussion

6.3.1 Rn-222 exhalation rates

222 226
Tables 6.1(a) and 6.1(b) present the Rn exhalation rate, Ra activity
222 226
concentration and Rn exhalation to Ra activity ratio for untreated sludge

piles, treated sludge strips, oil scales, sediments and barrel stored oily sludge.
222 222
Only emanometer Rn exhalation rates were used to determine the Rn to
226
Ra ratio for samples with both charcoal cups and emanometer values.
222
Table 6.1(a) displays Rn exhalation rates determined by both the charcoal

cups and the emanometer, which were generally similar and within

measurement uncertainties. A good linear correlation (R2 = 0.92) was also found

138
 between the emanometer and the charcoal cup readings (Figure 6.1), according

to the following correlation equation:

XEmanometer = (0.95 ± 0.05) XCharcoal Cup (6.1)

900
Emanometer 222Rn exhalation rate

750

600
(mBq m-2 s-1)

450

300

150

0
0 150 300 450 600 750 900

Charcoal cup 222Rn exhalation rate (mBq m-2 s-1)

Figure 6.1: Emanometer to charcoal cup readings correlation.

222
Table 6.1(b) displays Rn exhalation rates determined by only the

emanometer. Table 6.1(b) also includes the results from the additional bead and

sand samples, however these values were not included in the averages.

139
Table 6.1(a): 222Rn exhalation rate, 226Ra activity concentration and 222Rn to 226Ra
ratio for various petroleum industry radioactive wastes
222 222 226 222
Rn Rn Ra Rn:226Ra ratio
Sample ID (mBq m-2 s-1)c (mBq m-2 s-1)e (Bq kg-1) (mBq m-2 s-1/Bq kg-1)

Bahja untreated sludge piles

G01 579 ± 99 598 ± 79 2210 ± 40 0.27 ± 0.04
G02 316 ± 55 218 ± 35 1310 ± 20 0.17 ± 0.03
G03 303 ± 53 360 ± 47 2980 ± 30 0.12 ± 0.02
G04 249 ± 44 300 ± 40 2150 ± 70 0.14 ± 0.02
G05 301 ± 53 189 ± 24 2240 ± 40 0.08 ± 0.01
G06 691 ± 117 579 ± 69 4520 ± 50 0.13 ± 0.02
G07 325 ± 57 447 ± 49 4000 ± 40 0.11 ± 0.01
Bahja NORM store yard pit sludge
Gp1 45 ± 12 - 1245 ± 36 0.04 ± 0.01
Gp2 33 ± 9 - 1385 ± 36 0.02 ± 0.01
Nimr untreated sludge piles
N01 7.7 ± 3.0 39 ± 9 531 ± 13 0.07 ± 0.02
N02 14 ± 4 37 ± 7 403 ± 17 0.09 ± 0.02
N03 8.6 ± 3.4 26 ± 5 291 ± 14 0.09 ± 0.02
N04 16 ± 5 23 ± 5 314 ± 10 0.07 ± 0.02
N05 6.3 ± 2.8 19 ± 4 320 ± 11 0.06 ± 0.02
N06 52 ± 11 23 ± 4 285 ± 10 0.08 ± 0.02
N07 2.8 ± 2.1 15 ± 3 639 ± 17 0.024 ± 0.005
N08 - 16 ± 4 73 ± 7 0.22 ± 0.08
N09 - 76 ± 21 309 ± 19 0.25 ± 0.08

140
Table 6.1(a) (Continued): 222Rn exhalation rate, 226Ra activity concentration and
222
Rn to 226Ra ratio for various petroleum industry radioactive wastes
222 222
Rn Rn
226
Sample (mBq m -2
(mBq m-2 Ra 222Rn:226Ra ratio
ID s-1)c s-1)e (Bq kg ) -1
(mBq m-2 s-1/Bq kg-1)

N10 - 37 ± 9 284 ± 14 0.13 ± 0.04

N11 - 42 ± 10 361 ± 17 0.12 ± 0.03
N12 - 13 ± 3 327 ± 18 0.04 ± 0.01
N13 - 31 ± 8 339 ± 14 0.09 ± 0.03
N14 - 18 ± 4 334 ± 17 0.05 ± 0.02
Marmul untreated sludge piles
M02 4.3 ± 2.4 18 ± 11 36 ± 6 0.49 ± 0.38
M03 - 12 ± 7 42 ± 4 0.29 ± 0.20
M04 4.3 ± 2.4 12 ± 6 36 ± 4 0.33 ± 0.21
M05 - 17 ± 10 38 ± 4 0.44 ± 0.31
M06 13 ± 4 54 ± 17 125 ± 9 0.43 ± 0.17
M07 5.5 ± 2.6 14 ± 7 46 ± 6 0.30 ± 0.19
M08 56 ± 12 63 ± 16 918 ± 21 0.07 ± 0.02
M09 10 ± 4 27 ± 11 1022 ± 24 0.03 ± 0.01
M10 - 13 ± 8 27 ± 3 0.48 ± 0.37
M11 - 66 ± 18 146 ± 9 0.45 ± 0.15
M12 - 38 ± 9 196 ± 13 0.19 ± 0.06
M13 - 82 ± 20 3690 ± 60 0.02 ± 0.01
M14 - 155 ± 30 2290 ± 40 0.07 ± 0.01
c
Determined by charcoal cups
e
Determined by the emanometer

141
Table 6.1(b): 222Rn exhalation rate, 226Ra activity concentration and 222Rn to 226Ra
ratio for petroleum industry’s various radioactive wastes (emanometer
measurements only)

222 226 222

Rn Ra Rn:226Ra ratio
Sample ID (mBq m-2 s-1)e (Bq kg-1) (mBq m-2 s-1/Bq kg-1)

Bahja treated sludge strips

Strip # 005 23 ± 12 48 ± 6 0.48 ± 0.30
Strip # 008 10 ± 5 52 ± 6 0.19 ± 0.12
Strip # 039 20 ± 12 47 ± 6 0.42 ± 0.32
Nimr treated sludge strips
Strip # 001 37 ± 11 133 ± 8 0.28 ± 0.10
Strip # 024 10 ± 3 108 ± 7 0.09 ± 0.03
Strip # 026 14 ± 4 197 ± 10 0.07 ± 0.02
Strip # 044 35 ± 10 260 ± 10 0.14 ± 0.04
Strip # 045 19 ± 9 52 ± 5 0.36 ± 0.20
Strip # 061 22 ± 6 1340 ± 26 0.016 ± 0.004
Strip # 119 6±3 37 ± 5 0.15 ± 0.09
Marmul treated sludge strips
Strip # 015 12 ± 2 10 ± 1 1.23 ± 0.32
Strip # 018 34 ± 6 414 ± 13 0.08 ± 0.02
Strip # 020 12 ± 3 295 ± 19 0.04 ± 0.01
Strip # 027 13 ± 5 175 ± 9 0.08 ± 0.03
Strip # 031 7±3 79 ± 7 0.09 ± 0.04
Strip # 033 24 ± 5 205 ± 11 0.12 ± 0.03
Strip # 044 9±3 2080 ± 40 0.005 ± 0.002
Strip # 046 11 ± 4 455 ± 15 0.02 ± 0.01
Strip # 062 16 ± 4 115 ± 8 0.14 ± 0.05

142
Table 6.1(b) (Continued): 222Rn exhalation rate, 226Ra activity concentration and
222
Rn to 226Ra ratio for petroleum industry’s various radioactive wastes
(emanometer measurements only)
222 226 222
Rn Ra Rn:226Ra ratio
Sample ID (mBq m-2 s-1)e (Bq kg-1) (mBq m-2 s-1/Bq kg-1)

Scale samples
FHDOS 1 583 ± 66 4360 ± 50 0.13 ± 0.02
FHDOS 2 2760 ± 242 13000 ± 100 0.21 ± 0.02
FUDOS 3 274 ± 39 3380 ± 40 0.08 ± 0.01
FHDOS 4 1509 ± 156 11800 ± 100 0.13 ± 0.01
FHDOS 5 3209 ± 260 6340 ± 60 0.51 ± 0.05
FHDOS 6 5107 ± 415 17300 ± 100 0.30 ± 0.03
FHDOS 7 2779 ± 231 6380 ± 50 0.44 ± 0.04
Al-Noor evaporation pond sediments
NOR 1 102 ± 20 5260 ± 48 0.019 ± 0.004
NOR 2 108 ± 35 354 ± 13 0.31 ± 0.11
NOR 3 84 ± 35 119 ± 7 0.71 ± 0.34
NOR 4 120 ± 40 743 ± 16 0.16 ± 0.06
NOR 5 77 ± 31 379 ± 12 0.20 ± 0.09
NOR 6 31 ± 15 107 ± 6 0.29 ± 0.15
Barrel stored oily sludge, beads and sand
BHJB 1 152 ± 20 14000 ± 100 0.011 ± 0.001
BHJB 2 40 ± 7 1700 ± 30 0.023 ± 0.005
BHJB 3 79 ± 12 5560 ± 69 0.014 ± 0.002
BHJB 4 26 ± 5 2000 ± 40 0.013 ± 0.003
Beads 18 ± 3 38012 ± 131 0.0005 ± 0.0001
Sand 712 ± 87 35386 ± 162 0.020 ± 0.003
e
Determined by the emanometer

143
 A general upward trend was observed for 222Rn exhalation rate versus 226Ra

activity concentration (Figure 6.2). The overall slope and correlation coefficient

(R2) for 222

Rn exhalation rate to 226
Ra activity concentration were 0.095

± 0.014 mBq m-2 s-1/Bq kg-1 and 0.37, respectively. These results confirm a

general consensus between 222Rn exhalation and 226Ra activity concentration.

10,000.0
Bahja Strips
Rn exhalation rate (mBq m-2 s-1)

Bahja Piles
1,000.0

Nimr Strips

100.0 Nimr Piles

Marmul Strips

10.0 Marmul Piles

Al-Noor Sediments

1.0
222

Barrel Sludge

Scales
0.1
1 10 100 1,000 10,000 100,000

226
Ra activity concentration (Bq kg-1)

Figure 6.2: 222Rn exhalation rate versus 226Ra activity concentration.

Because radon emanation and its consequent exhalation is a random process,

depending upon multiple variables, it tends to follow a log-normal distribution

(refer to Section 6.1). Therefore, a summary of the exhalation data would be

better presented as a geometric mean rather than an arithmetic mean. However,

in this study; both arithmetic and geometric means have been presented.

Table 6.2 presents a summary of all of the measurements carried out in oilfields
222
of the Southern Oman Directorate. It includes Rn exhalation rate arithmetic

144
and geometric mean, along with the maximum and minimum measured values

for scales, evaporation pond sediments, barrel stored oily sludge, sludge piles,

sludge strips and ambient soil. It also contains the calculated arithmetic and
222 226
geometric mean Rn exhalation rate to Ra activity concentration ratio for

the samples.

Radon Exhalation Rate: Ambient soil radon exhalation rate measurements

were performed in Bahja, Al-Noor, Nimr and Marmul, and the arithmetic and

geometric mean values for the above locations were 3.7 ± 2.1 and

3.1 19..07 mBq m-2 s-1, respectively. For comparison purposes, six environmental

measurements of radon exhalation rates were also carried out in Jimboomba,

Queensland, Australia using activated charcoal cups. The calculated arithmetic

and geometric mean radon exhalation rates were 4.5 ± 0.7 and

4.3 53..91 mBq m-2 s-1, respectively. Given measurement uncertainties, the two

ambient soil 222Rn exhalation rates were similar.

222
The range, median and both arithmetic and geometric means of the Rn

exhalation rate for the six different sample types are illustrated in Figure 6.3.

Overall, the radon exhalation rates for the treated sludge strips were higher than

the rates for ambient soil, which can be attributed to the presence of 226Ra in the

sludge strips, introduced by mixing of sludge with clean soil. However, the

treated sludge strips exhalation rates ( 15 926 mBq m-2 s-1) were lower than for the

-2 -1 222
untreated sludge piles ( 47 154
15 mBq m s ). The Rn exhalation rate for the

scales was three orders of magnitude higher than the ambient soil, and barrel

145
stored oily sludge had comparable radon exhalations to the Al-Noor water pond

sediments.

226
Rn-222 Exhalation Rate to Ra Activity Concentration Ratio:

Figure 6.4 presents the range, median and both arithmetic and geometric means
222 226
of the Rn exhalation rate to Ra activity concentration ratio for the

individual sample types. Because of the potential affects of the log-normal

distribution of data and the modest sample size on F-statistics: the Kruskal-

Wallis non-parametric test, followed by Mann-Whitney post-hoc analysis was

used to compare sample median scores across the groups. The analysis showed
222 226
that the difference between the averages for the Rn exhalation rate to Ra

activity concentration ratio for ambient soil, treated and untreated sludge, scales
222
and pond sediments was not statistically significant. The geometric mean Rn
226
exhalation rate to Ra activity concentration ratio for treated sludge strips and

untreated sludge piles were comparable ( 0.10 00..37

03 and

-2 -1 -1
0.12 00..29
05 mBq m s /Bq kg , respectively), however the Bahja barrel stored

-2 -1 -1
oily sludge geometric mean ( 0.015 00..020
011 mBq m s /Bq kg ) was one order of

magnitude lower than the means for the rest of the samples and this difference

was found to be statistically significant (p < 0.05). As previously outlined in

Chapter 3, the collected sludge was either dry (if exposed to open sun for an

extended period of time) or oily (if recently removed from separation tanks or

stored in barrels). As such, the significantly lower 222Rn exhalation rate to 226Ra

activity concentration ratio for the Bahja barrel stored oily sludge might be a

result of its higher oily hydrocarbon content.

146
 The radon exhalation to radium concentration ratios for both pond sediments
-2 -1 -1
and scales ( 0.19 00..62 0.42
06 and 0.21 0.11 mBq m s /Bq kg , respectively) were about

twice those obtained for ambient soil, treated sludge and untreated sludge. In
226
pond sediments, the Ra (originating from produced water) is thought to be

present as a surface coating on the sediment grains, resulting in a non-uniform

222
distribution, which may explain the greater fraction of Rn emanation per
226
Ra activity concentration for the pond sediment samples. In contrast, a

uniform distribution of 226Ra is expected in the scale grains throughout the bulk

volume of the scale where it is contained within lattice of the barite or sulphite

(White and Rood, 2001), but because the scale grains are finer relative to sludge

grains, hence higher grain surface to volume ratio which may also explain the
222 226
greater fraction of Rn emanation per Ra activity concentration of the scale

samples.

147
Table 6.2: Arithmetic mean, geometric mean maximum and minimum 222Rn exhalation rates, and arithmetic and geometric means of 222Rn:226Ra
ratio for the various samples
Number 222
Rn 222
Rn:226Ra ratio
of
Sample type arithmetic mean a geometric mean b maximum minimum arithmetic meana geometric meanb
samples
(mBq m-2 s-1) (mBq m-2 s-1/Bq kg-1)

Scales 7 2317 ± 684 4635

1628 572 5107 274 0.26 ± 0.07 0.21 00..42
11

Al-Noor pond sediment 6 87 ± 14 80 132

49
120 31 0.28 ± 0.10 0.19 00..62
06

Barrel stored sludge 4 74 ± 33 59 129

27
152 26 0.015 ± 0.003 0.015 00..020
011

Bahja piles 9 309 ± 74 216 620

75
598 33 0.12 ± 0.03 0.10 00..21
05

Nimr piles 13 30 ±5 43
27 16 76 13 0.10 ± 0.02 0.08 00..16
05

Marmul piles 14 44 ± 12 73
31 13 155 12 0.28 ± 0.05 0.19 00..57
06

All pile samples 36 104 ± 27 47 154

15
598 12 0.17 ± 0.00 0.12 00..29
05

Bahja strips 3 18 ± 5 26
17 11 23 10 0.36 ± 0.11 0.34 00..56
21

Nimr strips 9 20 ± 5 17 829 37 6 0.16 ± 0.05 0.11 00..04

32

Marmul strips 7 15 ± 3 14 922 34 7 0.20 ± 0.14 0.07 00..32

02

All strip samples 19 18 ± 2 15 926 37 6 0.20 ± 0.02 0.10 00..37

03

148
Table 6.2 (Continued): Arithmetic mean, geometric mean maximum and minimum 222Rn exhalation rates, and arithmetic and geometric means of
222
Rn:226Ra ratio for the various samples

Number 222
Rn 222
Rn:226Ra ratio
of
Sample type arithmetic mean a geometric mean b Maximum Minimum arithmetic meana geometric meanb
samples
(mBq m-2 s-1) (mBq m-2 s-1/Bq kg-1)

Ambient soil 4 3.7 ± 2.1 3.1 19..07 8.2 0.7 0.13 ± 0.06 0.09 00..26
03

Ambient soilc 6 4.5 ± 0.7 4.3 53..91 6.3 2.9 - -

Beads 1 18 ± 3 d - - - 0.0005 ± 0.0001 d -

Sand 1 712 ± 87 d - - - 0.020 ± 0.003 d -

a
The errors reported are the arithmetic standard error
b
The upper and lower values geometric standard deviation from the geometric mean
c
Measurements carried out in Jimboomba, SE Queensland, Australia, included for comparison
d
Uncertainties represent counting error

149
 10000
95th percentile
90th percentile
75th percentile
Mean
Median
Geomean
25th percentile
1000
10th percentile
5th percentile
Rn exhalation rate (mBq m-2 s-1)

100
222

10

n=4 n = 19 n = 36 n=6 n=6 n=7

1
Barrel stored sludge
Ambient soil

Treated sludge strip

Scale
Untreated sludge pile

Pond sediment

Sample type

Figure 6.3: 222Rn exhalation rate range and averages for the various sample types.

150
 1
95th percentile
90th percentile
Ra activity concentration (Bq kg ) 75th percentile
-1

Mean
Median
Geomean
25th percentile
10th percentile
5th percentile
226

0.1
Rn exhalation rate (mBq m s ) /
-1
2
222

n=4 n=6 n = 36 n = 19 n=6 n=7

0.01
Scale
Ambient soil

Barrel stored sludge

Untreated sludge pile

Treated sludge strip

Pond sediment

Sample type

Figure 6.4: Ratio of 222Rn exhalation rate to 226Ra activity concentration range and
averages for the various sample types.

151
 Many authors have studied the effect of moisture content on radon

exhalation rate (Stranden et al., 1984, Hart and Levins, 1986, King and

Minissale, 1994, Shweikani et al., 1995, Sun and Furbish, 1995, Menetrez et al.,

1996, Nielson et al., 1996, Jha et al., 2000, Barillon et al., 2005, Faheem and

Matiullah, 2008), and they all agreed that as moisture content is increased,

radon exhalation rate increases to a maximum point, followed by a subsequent

decrease. This is because the presence of a small amount of water increases the

emanation rate by stopping the recoiled radon in the interstitial space, where

some of the additional stopped radon atoms would escape from water and

diffuse to the surface. However as the amount of water in the sample increases,

it leads to more radon getting trapped, and hence a decrease in the exhalation

rate.

It has been known since the early 1900s that radon is more soluble in

organic liquids than it is in water (Tanner, 1980), however there is no published

data available on the effect of hydrocarbon content on radon exhalation rate for

petroleum industry sludge. The results of this study suggest that samples with an
222
appreciable amount of oily hydrocarbon content tended to exhale less Rn,

which could be due to the fact that the higher the organic liquid content in the

sludge sample, the greater the proportion of recoiled radon that is absorbed and

retained.

152
6.4 Conclusions
222
Results of this study showed a direct relationship between Rn exhalation

and 226Ra activity concentration, along with a variation in 222Rn exhalation rates

up to three orders of magnitude for the various types of samples investigated.

222
The geometric mean of Rn exhalation rate for the surveyed samples, was

greatest for scales, followed by soil sediments, barrel stored oily sludge,
222
untreated sludge, treated sludge and ambient soil. The observed lower Rn

exhalation rates in treated sludge ( 15 926 mBq m-2 s-1), when compared to

-2 -1 226
untreated sludge ( 47 154
15 mBq m s ), can be attributed to the lower Ra

activity concentration in the treated sludge, as a result of mixing the sludge with

clean soil at the sludge farms.

222 226
An investigation of Rn exhalation rate and Ra activity concentration

ratios showed that apart from barrel stored oily sludge, there was no statistically

significant difference between the ratios for ambient soil and the rest of sample

types. The significant difference observed for barrel stored oily sludge is most

likely due to the absorption of radon in the liquid hydrocarbon organic content

of the barrel stored oily sludge.

No published data is currently available on the effect of hydrocarbon content

on radon exhalation rate for petroleum industry sludge and when coupled with

the complexity of radon exhalation, which is a function of multiple parameters,

it is evident that further experimental work is required to verify the relation

153
between radon exhalation rate and liquid hydrocarbon organic content of the

samples.

154
Chapter 7 SUMMARY AND CONCLUSIONS

7.1 Summary

This study is the first comprehensive assessment and evaluation of the

activity concentration, gamma dose rate and radon exhalation of large-scale

onshore petroleum operations in the Sultanate of Oman. It was carried out in the

arid desert terrain of an operational oil exploration and production region of

Oman, namely the Southern Oman Directorate (SOD), with the main locations

visited during the study being Al-Noor, Bahja, Nimr and Marmul.

This study focused on the radioactive waste products that are generated

during oil exploration and production. The assessment covered:

(i) Concentration of naturally occurring radionuclides;

(ii) External radiation dose rates in areas where waste products are

accumulated and disposed; and

(iii) Radon (222Rn) exhalation rates.

The types of activities covered included:

• Sludge recovery from separation tanks

• Sludge farming

• NORM storage

• Scaling in oil tubulars

• Scaling in gas production

• Sedimentation in produced water evaporation ponds

155
 Crude oil is usually co-produced with high salinity produced water, which

coexists with the crude oil in oil reservoirs. Because radium is soluble in water,

it is transported through oil production and processing installations as dissolved

radium in the produced water. It is then co-precipitated with calcium and

barium, in the form of carbonates and sulphates, as hard and highly insoluble

scale deposits on the interior walls of the pipes, and as sludge at the bottom of

separation tanks. In addition to increasing production costs, as a result of the

maintenance and downtime associated with scaled equipment replacement and

sludge removal, the scales also reduce efficiency by clogging valves, restricting

flow and damaging equipment.

After extraction, one of the disposal methods of the excess produced water

is pumping into evaporation ponds, and this waste water is contaminated by

NORM, heavy metals, volatile organic compounds, polycyclic aromatic

hydrocarbons and other toxic compounds. Evaporation concentrates the NORM

activity content of the produced water, which then crystallises and eventually

leads to scale formation on the ponds internal walls. Therefore, radium isotopes

were expected to be the major contributor to the activity in scale, sludge and

produced water evaporation pond sediments. Pb-210 was also expected to be

present in the older oil scales and sludge, as a result of ingrowth with the decay

of 226Ra.

For ease of interpretation, the results are provided in three separate tables.

Tables 7.1 (a-c) summarise findings for the identified radionuclide activity

concentrations (measured by both HPGe and portable NaI(Tl) gamma

156
spectrometers), gamma dose rates (measured by an energy compensated GM-

tube) and radon exhalation rates (measured by both charcoal cups and an

emanometer), respectively.

Table 7.1 (a) presents the range, median and mean radionuclide activity

concentrations for the various sample types. From the table it can be seen that

the gamma spectroscopy analysis of sludge, oil scale, gas scale and pond

sediment showed a large spectrum of radionuclides. These radionuclides are

progeny of the naturally occurring primordial series 238U, 235

U and 232
Th, along

with 40K. All activity concentrations were higher than the ambient soil level and

varied over several orders of magnitude.

210
The results also show excess activity of Pb in the oil scales, suggesting

that as well as being supported by 226Ra, mobilisation from oil reservoirs by the

produced water also took place. However the excess activity of 210Pb in the gas
226 222
scales is not supported by Ra, but is a result of Rn decay as it migrates in

the organic gaseous stream, and some authors have also suggested direct
210
mobilisation of Pb from the gas reservoir rock, in a process that is not yet

understood.

227
An interesting feature of our findings is the detection Ac, which was not
235
supported by U. During this study, Ac-227 was detected for the first time in

oil scales and sludge, however it was not detected in produced water

evaporation pond sediments, because it is most likely transported as a vector

and deposited with scale before reaching the ponds. Ac-227 half life

157
(21.8 years) is similar to that of 210Pb (22.3 years), but because it is unsupported

it would decay to ambient levels in seven to nine half lives. On the other hand,
226 210
the Ra supported Pb is a long term radiological hazard. Its activity
226
concentration will increase by ingrowth with Ra decay, reaching secular
226 226
equilibrium with Ra in about 100 years, and consequently decaying at Ra

half life of 1602 years.

226
The average oil scales Ra activity concentration (8.9 kBq kg-1) in Oman

fell within the lower end of the world wide range reported by other studies (0.1-

15,000 kBq kg-1). The stored sludge activity concentrations were also on par
226
with the world wide reported activities, and the Ra activity concentrations

were found to be similar to those reported for Australian uranium mining

activities.

228
The mean Ra:226Ra in sludge at time of deposition in a Nimr separation

tank was found to be 0.87 00..97

79 . The freshly removed sludge age calculated by

228
Th:228Ra activity ratio was 5.8 years, which was consistent with the industry’s

separation tank clearance frequency of 5 years. No correlation was observed

226 228
between sludge age and the Ra and Ra activity concentrations for each

individual farm, indicating the radioactivity levels had been consistent over the
228
years. Dating the oil and gas scales using the Th:228Ra activity ratio gave an

average age of 15 and 16 years, respectively.

158
Table 7.1 (a): Range median and mean activity concentrations of 226Ra, 210Pb, 228Ra, 228Th, 227Ac and 40K in Bq kg-1, for the various sample types
analysed in this study
Activity Concentrations Number
Median
Sample type (Range) Mean of
226 210 228 228 227 40
Ra Pb Ra Th Ac K samples

Sludge
6130
Stored in barrels (1700-223000)42160 - 4193
(1212-34413)9330 3680
(916-44639)10518 91
(15-614)188 952
(336-1480)897 6
Freshly removed 547
(363-985)588 - 243
(139-446)264 271
(186-496)296 - 118
(32-151)109 6
from separation tank
Untreated piles
3164
Bahja (1090-5670)3289 - 286
(92-470)261 344
(112-607)338 - 272
(182-954)427 25
323
Nimr (73-639)343 - 123
(55-270)129 113
(48-281)123 - 448
(134-595)433 14
Marmul a (27-3690)356 - (7-6036)394 (5-5164)342 - (47-720)360 16
Treated strips
54
Bahja (37-71)55 - 13
(8-20)14 10
(6-15)11 - 174
(107-258)175 12
Nimr b 47
(16-260)74 - 21
(8-130)34 20
(7-136)33 - 127
(75-369)146 16
Marmul strips b 67
(9.5-455)116 - 23
(1.9-130)41 26
(2.3-144)45 - 141
(16-467)163 29

159
Table 7.1 (a) (Continued): Range median and mean activity concentrations of 226Ra, 210Pb, 228Ra, 228Th, 227Ac and 40K in Bq kg-1, for the various
sample types analysed in this study
Activity concentrations Number
Median
Sample type (Range) Mean of
226 210 228 228 227 40
Ra Pb Ra Th Ac K samples

Oil tubular 6380

(3380-17300)8940 4720
(3060-7590)4920 2250
(1360-4310)2510 2920
(1930-6810)3730 67
(34-123)64 - 7
scales
Gas tubular 83
(22-125)75 42716
(959-66405)30561 19
(2.3-32)17 35
(2.9-48)26 22
(4-181)46 94
(26-347)133 12
scales
Produced water
367
evaporation (107-5260)1160 - 41
(10-583)127 13
(5-205)46 - 286
(30-837)330 6
sediments
34
Ambient soil (27–41)34 - 8
(6-11)8 7
(6-9)7 - 110
(93-293)151 4
a
area weighted mean values are reported due to distinct low and high radioactivity sections
b
excluding hotspots

160
 Field surveys of gamma radiation dose rates were carried out in open spaces

where ‘sludge farming’ occurred. Sludge farming is the name given to the

biodegradation process which utilises naturally occurring micro-organisms to

reduce the complex hydrocarbon components of sludge into carbon dioxide and

water. This process occurs after the sludge has been mixed with clean soil and

has undergone frequent tilling and watering. The difference in radioactivity

concentrations between untreated and treated sludge is evident from the values
226
presented in Table 7.1 (b). Despite obtaining a Ra mean activity

concentration and 222Rn exhalation rate at least two times and five times higher

than the ambient soils, respectively (Table 7.1 (a and c)), the treated sludge strip

gamma dose rate averages were close to the ambient soil levels, although some

‘spots’ were detected at Nimr and Marmul sludge farms, which gave higher

gamma dose rates. The reason for this discrepancy in activity concentration and

radon exhalation rate to gamma dose rate averages might be due to the finite

thickness (40 ± 10 cm) of the treated layer of sludge. Therefore, the gamma

dose rate readings cannot be used as a reliable indicator in the assessment of the

radiological contamination of treated sludge.

161
Table 7.1 (b): Mean (± standard deviation), median and range of gamma dose
rates in µSv h-1 for untreated and treated sludge in Bahja, Nimr and Marmul
sludge farms, and ambient soil readings
Sample type Dose rates (µSv h-1) Number
Mean Median Range of readings
Untreated sludge piles
Bahja 0.702 ± 0.250 0.637 0.281 - 1.116 23
Nimr 0.166 ± 0.026 0.166 0.126 – 0.238 14
Marmul 0.345 ± 0.454 0.146 0.072 – 1.781 16
Treated sludge strips
Bahja 0.084 ± 0.004 0.084 0.076 – 0.091 12
Nimr 0.109 ± 0.084 0.080 0.072 – 0.426 17
Marmul 0.115 ± 0.068 0.091 0.063 – 0.362 31
Ambient soil 0.086 ± 0.014 0.082 0.074 - 0.105 4

Table 7.1 (c) presents 222Rn exhalation rates and radon exhalation to radium

concentration ratios for the various samples analysed in this study. The

geometric mean of ambient soil exhalation rate for area surrounding the sludge

was 3.1 19..07 mBq m-2 s-1. Radon exhalation rates reported in oil waste products

were all higher than the ambient soil value and varied over three orders of
226
magnitude. Rn-222 exhalation to Ra concentration ratios for sludge farm

treated and untreated sludge were similar to the ambient soil value, whereas the

oil scale and pond sediment values were twice as high. The reason for this

difference might be that the scale grains are finer than the sludge grains,
226
resulting in a higher emanation fraction. In the pond sediment, the Ra

(originating from produced water) is thought to be present as a surface coating

on the sediment grains, resulting in a non-uniform distribution, which may

explain the greater fraction of 222Rn emanation per 226Ra activity concentration.

162
In contrast, the oily sludge had a low radon exhalation to radium concentration

ratio. Because radon is known to be soluble in water and organic liquids, the

results suggest a greater proportion of recoiled radon in the oily sludge samples

is absorbed and retained, hence resulting in the lower 222Rn:226Ra ratio.

163
Table 7.1 (c): Maximum, minimum and geometric mean of 222Rn exhalation rates in mBq m-2 s-1 and the geometric mean of radon exhalation to
radium concentration ratio in mBq m-2 s-1/Bq kg-1 for the various sample types analysed in this study
222
Sample type Rn exhalation rate(mBq m-2 s-1) 222
Rn:226Ra ratio Number

Maximum Minimum Geomean Geomean of readings

4635
Oil scales 5107 274 1628 572 0.21 00..42
11 7

Pond sediments 120 31 80 132

49 0.19 00..62
06 6

Untreated sludge piles 598 12 47 154

15 0.12 00..05
29
36

Treated sludge strips 37 6 15 926 0.10 00..37

03 19

Barrel stored sludge 52 26 59 129

27 0.015 00..020
011 6

Ambient soil 8.2 0.7 3.1 19..07 0.09 00..26

03 4

164
 A total of five site visits, each ranging from 3-17 days, were made for in-situ

measurements and sample collection. Due to a number of difficulties, only a

limited amount of time could be spent in the field. For example, limited

transport was available for both the 260 kg of equipment and researchers to get

to the site, and finding accommodation in the remote mining camps was not

always easy. Also, in order to avoid transporting the radioactive materials back

to Australia, all of the collected samples had to be analysed in the Medical

Physics Laboratory of Sultan Qaboos University (SQU), Muscat, using both the

SQU facilities and the equipment transported from QUT.

Many factors also needed to be taken into consideration when designing the

measurement and analysis procedures used in the study. For example, where

portable gamma spectroscopy is used for detecting activity concentration of

228
Ra through its progeny, it was important to understand that, in petroleum
228
waste products, its immediate daughter, Th, is found in transient rather than
228
secular equilibrium with Ra, while in ambient soils, the equilibrium is

secular.

Despite these difficulties, many of the features of this study are novel and

unique. Firstly, most of the previously published studies relate to offshore

operations. Therefore this study is unique in being the first large-scale onshore

study on petroleum exploration and production radiological assessment and in

being conducted in the Sultanate of Oman. Therefore, the information provided

in this thesis may be used as an important reference for NORM activity

concentration assessments in the oil industry. In addition, because this study

165
was conducted in the Southern Oman Directorate, the findings would also be a

good source of knowledge for possible future assessments in oil rig operations

of the Northern Oman Directorate as well.

Further, this was the first ever study to perform an assessment of radon

(222Rn) exhalation from oil sludge samples. It was also the first ever study to

quantify the presence of 227Ac in oil sludge and scales, and to date, it is only the
227
second study to ever quantify the presence of Ac in gas scales. Ac-227 has
226 228
high inhalation and ingestion dose coefficients compared to Ra, Ra and
210
Pb, particularly since its committed effective dose coefficient for inhalation is
226 228 210
two orders of magnitude higher than Ra, Ra and Pb. Therefore, proper

radiological protection measures should be adhered to during the

decontamination of scaled pipes, as well as during the disposal of scale and

sludge.

An empirical relation was also derived between petroleum sludge activity

concentrations and gamma dose rates. The coefficients of this relationship

turned out to be different to those reported by various authors who investigated

such relationships of infinite thickness and infinite dimension slabs of soils. The

reasons for the lower conversion coefficients obtained in this study are thought

to be due to: (1) the presence of heavy metal sediments and corrosive particles

in the petroleum sludge, leading to a greater attenuation coefficient; (2) the

radionuclides may not have reached equilibrium at the time of measurement;

(3) the ambient soil measurements are usually conducted on flat extended land,

whereas untreated sludge piles are in small heaps; and (4) the greater soil

166
density of ambient soil compared to less compacted untreated and treated

sludge.

7.2 Future directions

As outlined above, this was the first ever study to perform an assessment of

radon (222Rn) exhalation from oil sludge samples, and the results of this study

suggest the samples with an appreciable amount of oily hydrocarbon content

tended to exhale less 222Rn. As such, further investigations are recommended to

establish this hypothesis. In addition, Ac-227 was detected for the first time in

oil scales and sludge, possibly as a result of the residues left behind from the

produced water. However, further investigations into the formation and ultimate

fate of Ac-227 are also required, in order to develop a better understanding of its

presence in the petroleum industry.

It is well known that the measurement capabilities of HPGe systems vary

significantly, and unfortunately, the SQU pop-up detector used in this study had
210
a poor sensitivity for the Pb gamma energy of 46.5 keV, resulting in high

uncertainties and/or no detection of 210Pb in a number of samples. As such, it is

recommended that future studies use a planner HPGe system instead, in order to

increase the detection capabilities for 210Pb.

Scaling sedimentation and deposition in various sections of the extraction,

transport and storage equipment is a major problem in the petroleum industry,

costing the oil production companies significant time and money, due to

167
maintenance and replacement costs, as well as losses in efficiency and the down

time associated with its removal. Thus, the ability to section the scale, and
228
measure the age of individual sections (using Ra:226Ra and/or 228
Th:228Ra

activity ratios) would contribute greatly to existing knowledge on the scale

deposition process. However, field conditions during this study were such that

sectioning the depositions was not possible, leaving many opportunities for

further measurements and analysis in the future.

To summarise, the findings of this study highlight that considerably more

work is still required and that there are many gaps in knowledge yet to be

explored, including:

• Radiological health impact due to the petroleum mining activities

• Investigation of dust re-suspension pathway in the arid desert

environment

• Investigation of the social aspects of bedwen life style to model the

likely radiation dose to critical groups in the long term

• Modelling the likely radiation dose to be incurred by direct gamma,

inhalation and injection pathways during future oil and gas scale

removal activities

• Further investigation on 227Ac migration, deposition and fate in the oil

and gas systems

• Investigation of scale deposition rate by use of inherent radiological

behaviour of 228Ra:226Ra and/or 228Th:228Ra activity ratio(s)

168
 220 228
• Assessment of Rn activity flux, since the presence of Ra may

make it an inhalation hazard, especially in confined areas such as

separation tanks

• Measurement of 220Rn and 222Rn in the air

• Use of a planner HPGe system for improved detection of 210Pb

210
• Detection of Po and its applications for health hazard and/or

estimating the age of 210Pb depositions

• Determination of petroleum samples moisture and hydrocarbon

content and its implications on radon exhalation

• Determination of sample mineralogy using X-ray fluorescence

spectrometer (XRF) and diffractometer (XRD)

169
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