Engineering Encyclopedia

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Oil Industry Applications Of Aas/Aes Techniques

Note: The source of the technical material in this volume is the Professional
Engineering Development Program (PEDP) of Engineering Services.
Warning: The material contained in this document was developed for Saudi
Aramco and is intended for the exclusive use of Saudi Aramco’s
employees. Any material contained in this document which is not
already in the public domain may not be copied, reproduced, sold, given,
or disclosed to third parties, or otherwise used in whole, or in part,
without the written permission of the Vice President, Engineering
Services, Saudi Aramco.

Chapter : Laboratory For additional information on this subject, contact

File Reference: LAB10607 J. F. Bormans on 876-4033
Engineering Encyclopedia Laboratory
Oil Industry Applications of ASS/AES Techniques

Contents Pages

IDENTIFYING APPLICATIONS OF AAS/AES TECHNIQUES TO OIL

INDUSTRY WATER SAMPLES............................................................................ 1
Fluids Correlations ....................................................................................... 1
Water Compatibilities................................................................................... 4
Scaling Studies ............................................................................................. 5
Corrosion Studies ......................................................................................... 5
Environmental Applications ......................................................................... 6
IDENTIFYING APPLICATIONS OF AAS/AES TECHNIQUES TO OIL
INDUSTRY OIL SAMPLES ................................................................................... 8
Elemental Analyses of Crude Oil ................................................................. 8
Lube Oil Analyses ........................................................................................ 9
IDENTIFYING APPLICATIONS OF AAS/AES TECHNIQUES TO OIL
INDUSTRY SOLID SAMPLES ............................................................................ 10
Metal Samples ............................................................................................ 10
Geologic Samples....................................................................................... 10
Unknown Solids ......................................................................................... 10
WORK AID 1: DATA BASES AND PROCEDURE TO IDENTIFY
APPLICATIONS OF AAS/AES TECHNIQUE FOR OIL INDUSTRY
SAMPLES ............................................................................................................. 11
Data Bases .................................................................................................. 11
2. Data Base: Vanadium and Nickel of Residues Above 343° C From
Some Export Crudes................................................................................... 12
Procedure.................................................................................................... 13
REFERENCE......................................................................................................... 14

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Engineering Encyclopedia Laboratory
Oil Industry Applications of ASS/AES Techniques

IDENTIFYING APPLICATIONS OF AAS/AES TECHNIQUES TO OIL INDUSTRY

WATER SAMPLES

Water samples can be analyzed by AAS/AES with little or no sample preparation. Water
sample preparation may be as simple as dilution with deionized water or filtering to
eliminate background interferences. More complicated sample preparation for water
samples include extractions with chelating agents and addition of reagents to form
compounds that behave better in the atomization process. Instrument manufacturers and
the standard methods manuals describe these sample preparations for certain samples.

Fluids Correlations

A good water analysis can give definitive information for correlating zones between wells.
A water pattern (Stiff Diagram) drawn from laboratory data can match two waters. The
diagrams are drawn from a major constituent analysis that includes Na, Ca, and Mg that
are often determined by AAS. Figure 1, ABU SA’FAH Field Geochemical Water
Analysis, shows the Stiff Diagrams for waters from Wells #26, #31, #50 and #17. The
patterns clearly indicate that Well #50 is a different water.

During the drilling process, drill-stem test samples are sometimes recovered for water
analysis. A well log analysis may indicate that a particular formation correlates to a zone
in an offset well, but the water analysis provides confirmation.

The same type of water correlation tests have been used to determine if the water sample
collected from a drill-stem test is actually formation water or mud filtrate. An analysis of a
mud filtrate sample is compared to the test sample analysis.

In cases of brine contamination of a fresh water supply, the source of the brine may be
identified by trace metals or Stiff Diagrams.

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Oil Industry Applications of ASS/AES Techniques

Abu Sa’ Fah Field

Geochemical Water Analyses
Stiff Diagram as Fingerprint

Water Patterns - me/l

Standard
30 20 10 0 10 20 30 40
1000 Na Cl 100
100 Ca HCO 1
10 Mg SO 10
1 Fe CO
Well #26
Water Patterns - me/l
Standard
20 10 0 10 20
1000 Na Cl 100
100 Ca HCO 1

10 Mg SO 10

1 Fe CO
Well #50

Water Patterns - me/l

Standard
30 20 10 0 10 20 30 40
1000 Na Cl 100
100 Ca HCO 1
10 Mg SO 10
1 Fe CO
Well #31

Water Patterns - me/l

Standard
30 20 10 0 10 20 30 40
1000 Na Cl 100
100 Ca HCO 1
10 Mg SO 10
1 Fe CO
Well #17

Figure 1

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Geochemists have used elemental analyses of brines associated with petroleum to study
oil migration and accumulation in reservoirs. Figure 2, Average Elemental Composition of
Oilfield Waters, illustrates the variations in water composition with the geologic age.

Average Elemental Composition of Oilfield Waters

Tertiary Cretaceou Jurassi Permian Cambrian

ELEMEN s c
T mg/L mg/L mg/L
mg/L mg/L
Li 4 4 400 3 17
Na 39,000 31,000 120,000 47,000 23,400

K 220 130 900 170 440

Rb 0.24 0.10 0.10 0.80 3.3

Cs 0.20 0.10 0.10 0.13 0.6

Ca 2,530 7,000 56,300 8,600 4,000

Mg 530 900 2,500 2,000 1,300

Sr 130 200 320 7 125

Ba 60 40 10 8 -

B 36 20 13 0.88 7

Cu 0.63 - - - -

Figure 2

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Water Compatibilities

In field situations that involve mixing waters from different sources, analyses are
necessary to determine if the waters are compatible. A produced brine containing a high
Ba concentration may be stable until mixed with a water of high sulfate concentration. An
example is shown in Figure 3, Analysis for Compatibility. The two waters were produced
in the same field, but from two separate reservoirs. The sand stone reservoir water
contained barium and the limestone water contained sulfate. When mixed, the barium
sulfate precipitation became a big problem.

Analysis for Compatibility Study

Ion Sandstone Reservoir Limestone Reservoir

mg/L mg/L
Ca 2,434 2,988

Mg 897 1,089

Ba 220 7

Sr 168 199

SO 4 17 346

Figure 3

Water to be injected into producing oil field reservoirs should be compatible with the
connate water and the formation. Formation damage could occur if precipitates such as
BaSO are formed in-situ. Permanent damage can also occur in clay bearing formations. If
4

fresh water is injected into a formation that originally had saline connate water, clay
minerals can swell and permanently shut-off the reservoir porosity. AAS/AES analyses
can be applied to determine compatibility of injection water.

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Scaling Studies

Complete water analyses of produced brine samples are needed to predict scaling
tendencies in the field. Elaborate computer programs have been devised to predict if scale
inhibitor chemicals will be needed. These programs rely on accurate analyses by
AAS/AES.

Evaluation of scale inhibitor chemicals involves analysis of samples to determine the

decrease of the barium or calcium from solution. Simple bottle tests of varying amounts of
inhibitor in series are allowed to equilibrate for several days. Determinations of Barium or
calcium left in solution indicate the amount of scale that precipitated. The optimum
inhibitor chemical and treating concentration for a water source can be found.

Corrosion Studies

Assistance in solving corrosion problems can often be given by atomic spectroscopy. Iron
concentration data in water above and below treating points can aid the metallurgist in
evaluating the treating chemical.

Bottle tests for corrosion inhibitors can also be evaluated by measuring the iron in
solution.

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Environmental Applications

AAS and AES are the recognized techniques for analysis of the toxic heavy metals.
Methods have been published for environmental monitoring of industrial waste water,
offshore discharges and drinking water samples. Leachates of solid wastes are also
analyzed for toxic metals by AAS and AES.

The very low detection limits for graphite furnace AAS, cold vapor AA, and plasma
emission have made these techniques the accepted methods for determining toxic metals.
Figure 4 is a table published by Perkin-Elmer Corporation showing the detection limits for
selected elements using their AAS/AES instruments.

Typical Detection Limits, µg/L (for AAS/AES)

ELEMENT FLAME AA GFAA ICP HYDRIDE

Aluminum 30.0 0.01 20.0
Arsenic 140 0.2 50.0 0.02
Barium 8.0 0.04 0.5
Boron 700 15 4.0
Cadmium 0.5 0.003 4.0
Chromium 2.0 0.01 5.0
Cobalt 6.0 0.02 6.0
Copper 1.0 0.02 3.0
Iron 3.0 0.02 3.0
Lead 10.0 0.05
Mercury 170 2.0 0.001
Molybdenum 30.0 0.02 8.0
Nickel 4.0 0.1 10.0
Selenium 70.0 0.5 50.0 0.02
Silicon 60.0 0.1
Silver 0.9 0.005
Vanadium 40.0 0.2 5.0
Zinc 0.8 0.001 4.0

Figure 4

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The toxic limits for heavy metals in drinking water are shown in Figure 5, U.S.
Environmental Protection Agency Primary Drinking Water Standards. Note that the
detection limits in Figure 4 are µg/L and the contaminant levels in Figure 5 are mg/L.
Both units are commonly used in the literature and the analyst must be aware of this when
comparing data.

U. S. Environmental Protection Agency

Primary Drinking Water Standards for Metals

CONTAMINANT MAX CONTAMINANT

LEVEL
mg/L
Ag 0.05

As 0.05

Ba 1.

Cr 0.05

Hg 0.002

Na 20

Pb 0.05

Se 0.01

Figure 5

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Oil Industry Applications of ASS/AES Techniques

IDENTIFYING APPLICATIONS OF AAS/AES TECHNIQUES TO OIL INDUSTRY

OIL SAMPLES

Oil samples can be analyzed routinely by AAS/AES by either direct introduction into the
atomization source, or introduction after a pre-treatment. The pre-treatment may be as
simple as dilution with a suitable solvent such as toluene. A less simple pre-treatment
involves ashing the sample and dissolving the residue in an aqueous acid solution. The
ashing technique is used to concentrate trace metals and to avoid setting up the instrument
with a special organics burner or torch. Detailed procedures for these sample preparations
are found in instrument manufacturers’ manuals and published standard methods.

Elemental Analyses of Crude Oil

Figure 6, Trace Elements in Crudes, shows some examples of the amounts of trace metals
found in crude oil samples.

TRACE ELEMENTS IN CRUDES

California Libya Venezuela Alberta

ELEMEN mg/L mg/L mg/L mg/L
T
As 0.655 0.077 0.284 0.0024
Cd 0.004 - - -
Co 13.5 0.032 0.178 0.054
Cr 0.640 0.0023 0.430 -
Cu 0.93 0.19 0.21 -
Fe 68.9 4.94 4.77 0.696
Hg 23.1 - 0.027 0.084
Mn 1.20 0.79 0.21 0.048
Ni 98.4 49.1 117 0.609
Se 0.364 1.10 0.369 0.0094
V 7.5 8.2 1110 0.682
Zn 9.76 62.9 0.692 0.670

Figure 6

Crude oils contain organometallic compounds that can be correlated to the origin and age
of the crude. Petroleum geologist often use AAS or AES metal determinations in
geochemical basin evaluations.

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Metals such as Ni and V are concentrated in crude oils in the forms of porphyrins. These
metals are routinely determined by AAS in crudes prior to refining. Ni and V are
detrimental to the catalysts used in the catalytic cracking process in refineries.

The heavy metals have been suggested as identifiers of crude oil spills on land or at sea.
Each crude has a characteristic trace element signature.

Lube Oil Analyses

Many refinery support laboratories perform wear metals analyses in lube oil. The amount
of iron suspended in a used oil is indicative of the wear on the engine parts. AAS and AES
methods are both commonly used for such determinations.

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Oil Industry Applications of ASS/AES Techniques

IDENTIFYING APPLICATIONS OF AAS/AES TECHNIQUES TO OIL INDUSTRY

SOLID SAMPLES

Solid samples can be directly analyzed only by arc and spark AES and by graphite furnace
AAS. In actual practice, however, solid samples are routinely analyzed by all AAS/AES
techniques after dissolution. Solid samples are either dissolved in deionized water, strong
aqueous acids or converted to soluble salts by ashing or chemical reaction. These
techniques are described in detail in such books as Standard Methods for the Examination
of Water and Wastewater, American Public Health Association.

Metal Samples

Analysis of the composition of metals is useful to the metallurgist. Stainless steel types
may be identified by compositional analysis. Mixing stainless steel types in a single piece
of equipment can cause stress failures. Analysis of corrosion products provides data to
study the corrosion problem.

Refinery catalyst are heavy metals. Refinery engineers studying catalyst application and
efficiency require analyses of the catalyst materials. Such analyses can be performed by
AAS/AES methods.

Geologic Samples

Rock samples, drill cuttings or core samples may be analyzed by AAS/AES to provide the
geochemist additional data in identifying reservoir formations. Assays for precious metals
may also be performed by AAS/AES.

Unknown Solids

Often the operations support laboratory is asked to identify a material recovered from an
operating environment. These are called “whatsit” samples by the chemical analyst. The
operating engineer does not always describe the problem or reason for requesting an
analysis. Before working on such samples, the analyst should call the requestor and ask as
many questions as necessary to determine what information is needed to solve his
problem. If elemental analysis is required, AAS or ICP can be most useful.

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WORK AID 1:DATA BASES AND PROCEDURE TO IDENTIFY APPLICATIONS OF

AAS/AES TECHNIQUE FOR OIL INDUSTRY SAMPLES
Data Bases

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2. Data Base: Vanadium and Nickel of Residues Above 343° C From Some Export
Crudes

Crude oil Vanadium Nickel V / Ni

(Source) ppm ppm Ratio
Bachaquero 484 61 7.9
(Venezuela)
Basara Light 38 12 3.2
(Iraq)
Bonny Medium 2 15 0.13
(Nigeria)
Forties 9 4 2.2
(UK Offshore)
Safaniya 95 30 3.2
(Saudi Arabia)
Zarzaitine 4 2 2.0
(Algeria)

3. Data Base: Composition of Standard Stainless

AISI TYPE
ELEMENT 304 305 310 316
% Cr 18 - 20 17 - 19 24 - 26 16 - 18
% Ni 8 - 10.5 10.5 - 13 10 - 14 10 - 14
% Mn 2.0 2.0 2.0 2.0
% Mo - - - 2.0 - 3.0
% Si 1.0 1.0 1.5 1.0
%C 0.08 0.12 0.25 0.08
%P 0.045 0.045 0.045 0.045
%S 0.030 0.030 0.030 0.030
%N 0.010 - - 0.010

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Procedure

1. Identify the purpose for the data.

a. Correlation of waters
b. Water compatibility
c. Corrosion or scale study
d. Environmental monitoring
e. Other

2. Identify the sample preparation needed and determine the concentration range for
the elemental analysis.

a. No sample preparation
b. Dilution with deionized water
c. Other

3. Identify accuracy required for the data to satisfy its purpose and identify the
AAS/AES techniques that will produce that accuracy.

a. Flame AAS (See Module 106.02).

b. GFAAS (See Module 106.02).
c. Mercury vapor or hydride generation AAS (See Module 106.02).
d. ICP or DCP (See Module 106.04).

4. Identify the time required to obtain the data.

a. Fast analysis
b. Slow analysis

5. Identify the single best AAS/AES analytical procedure for the sample analysis.

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REFERENCE

“API Recommended Practice for Analysis of Oil-Field Waters”, 1981, (API RP 45),
American Petroleum Institute, Dallas, TX, USA.

Boss, Charles B., and Kenneth J. Fredeen, Concepts, Instrumentation, and Techniques in
Inductively Coupled Plasma Atomic Emission Spectrometry, 1989, The Perkin Elmer
Corporation, USA.

Butt, J. A., D. F. Duckworth and S. G. Perry, 1986, Characterization of Spilled Oil

Samples, The Institute of Petroleum, London, by John Wiley & Sons, Chichester.

Douglas A. Skoog, Principles of Instrumental Analysis, 1985, Saunders College

Publishing, New York, NY, USA.

Keenan, Charles W., Jessie H. Wood, and Donald C. Kleinfelter, General College
Chemistry, 1976, Harpers and Row Publishers, New York, NY, USA.

Richard D. Beaty, Concepts Instrumentation and Techniques in Atomic Absorption

Spectrophotometry, 1988, The Perkin Elmer Corporation, USA.

Standard Methods for the Examination of Water and Wastewater, 1985, American Public
Health Association, Washington, DC, USA.

Valdo Valkovic, 1978, Trace Elements in Petroleum, The petroleum Publishing Company,
Tulsa, Oklahoma, USA.

Willard, Hobart H., Lynne L. Merrit, Jr., John A. Dean, and Frank A. Settle, Jr., 1988,
Instrumental Methods of Analysis, Wadsworth Publishing Company, Belmont, CA, USA.

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