Designation: D8056 − 16

Standard Guide for

Elemental Analysis of Crude Oil1
This standard is issued under the fixed designation D8056; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope D3230 Test Method for Salts in Crude Oil (Electrometric

1.1 This guide summarizes the current information about Method)
the test methods for elemental and associated analyses used in D4057 Practice for Manual Sampling of Petroleum and
the analysis of crude oils. This information can be helpful in Petroleum Products
trade between the buyers and sellers of crude oil. Elemental D4177 Practice for Automatic Sampling of Petroleum and
analyses tests form an important part of quantifying the crude Petroleum Products
oil quality. D4294 Test Method for Sulfur in Petroleum and Petroleum
Products by Energy Dispersive X-ray Fluorescence Spec-
1.2 The values stated in SI units are to be regarded as the
standard. No other units of measurement are included in this trometry
standard. D4629 Test Method for Trace Nitrogen in Liquid Petroleum
Hydrocarbons by Syringe/Inlet Oxidative Combustion and
1.3 This standard does not purport to address all of the Chemiluminescence Detection
safety concerns, if any, associated with its use. It is the
D4929 Test Methods for Determination of Organic Chloride
responsibility of the user of this standard to establish appro-
Content in Crude Oil
priate safety and health practices and determine the applica-
D5185 Test Method for Multielement Determination of
bility of regulatory limitations prior to use.
Used and Unused Lubricating Oils and Base Oils by
2. Referenced Documents
2.1 ASTM Standards:2 http://qstandard.org/
D129 Test Method for Sulfur in Petroleum Products (Gen-
Inductively Coupled Plasma Atomic Emission Spectrom-
etry (ICP-AES)
D5291 Test Methods for Instrumental Determination of
Carbon, Hydrogen, and Nitrogen in Petroleum Products
eral High Pressure Decomposition Device Method) and Lubricants
D482 Test Method for Ash from Petroleum Products
D5708 Test Methods for Determination of Nickel,
D1548 Test Method for Vanadium in Heavy Fuel Oil1
Vanadium, and Iron in Crude Oils and Residual Fuels by
(Withdrawn 1997)3
Inductively Coupled Plasma (ICP) Atomic Emission
D1552 Test Method for Sulfur in Petroleum Products by
Spectrometry
High Temperature Combustion and IR Detection
D2622 Test Method for Sulfur in Petroleum Products by D5762 Test Method for Nitrogen in Petroleum and Petro-
Wavelength Dispersive X-ray Fluorescence Spectrometry leum Products by Boat-Inlet Chemiluminescence
D3227 Test Method for (Thiol Mercaptan) Sulfur in D5854 Practice for Mixing and Handling of Liquid Samples
Gasoline, Kerosine, Aviation Turbine, and Distillate Fuels of Petroleum and Petroleum Products
(Potentiometric Method) D5863 Test Methods for Determination of Nickel,
D3228 Test Method for Total Nitrogen in Lubricating Oils Vanadium, Iron, and Sodium in Crude Oils and Residual
and Fuel Oils by Modified Kjeldahl Method Fuels by Flame Atomic Absorption Spectrometry
D6259 Practice for Determination of a Pooled Limit of
Quantitation for a Test Method
1
This guide is under the jurisdiction of ASTM Committee D02 on Petroleum
D6299 Practice for Applying Statistical Quality Assurance
Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcom- and Control Charting Techniques to Evaluate Analytical
mittee D02.03 on Elemental Analysis. Measurement System Performance
Current edition approved July 1, 2016. Published July 2016. DOI: 10.1520/
D8056-16.
D6470 Test Method for Salt in Crude Oils (Potentiometric
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or Method)
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM D6792 Practice for Quality System in Petroleum Products
Standards volume information, refer to the standard’s Document Summary page on and Lubricants Testing Laboratories
the ASTM website.
3
The last approved version of this historical standard is referenced on D7260 Practice for Optimization, Calibration, and Valida-
www.astm.org. tion of Inductively Coupled Plasma-Atomic Emission

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 D8056 − 16
Spectrometry (ICP-AES) for Elemental Analysis of Petro- been found in crude oils (1).6 Generally, sulfur and nitrogen are
leum Products and Lubricants the two most abundant elements found in crude oils except for
D7343 Practice for Optimization, Sample Handling, carbon and hydrogen. Most other inorganic elements are
Calibration, and Validation of X-ray Fluorescence Spec- present at trace levels (mg/kg). Sulfur, nitrogen, vanadium,
trometry Methods for Elemental Analysis of Petroleum nickel, and iron are the most frequently determined elements in
Products and Lubricants the crude oils. Ratios such as vanadium to vanadium + nickel,
D7372 Guide for Analysis and Interpretation of Proficiency and iron to vanadium are suggested as being useful for oil type
Test Program Results characterizations. Since organometallic compounds are con-
D7455 Practice for Sample Preparation of Petroleum and centrated in the heavy ends of petroleum, transition element
Lubricant Products for Elemental Analysis concentrations and ratios can serve as excellent oil-oil corre-
D7482 Practice for Sampling, Storage, and Handling of lation parameters. Generally, vanadium and nickel content
Hydrocarbons for Mercury Analysis increases with asphaltic content of crude oil (API gravity is an
D7578 Guide for Calibration Requirements for Elemental indicator). Lighter crude oils contain lesser amounts of metals
Analysis of Petroleum Products and Lubricants (2, 3).
D7621 Test Method for Determination of Hydrogen Sulfide 3.3 Metal complexes called porphyrins are a major compo-
in Fuel Oils by Rapid Liquid Phase Extraction nent of metallic compounds in crude oils. The principal
D7622 Test Method for Total Mercury in Crude Oil Using porphyrin complexes are Ni+2 and VO+2 compounds. There are
Combustion and Direct Cold Vapor Atomic Absorption also other non-porphyrin complexes and other metallic com-
Method with Zeeman Background Correction pounds present in crude oils (4, 5).
D7623 Test Method for Total Mercury in Crude Oil Using
Combustion-Gold Amalgamation and Cold Vapor Atomic 3.4 Some typical literature citations in this area are included
Absorption Method in the reference section at the end of this guide.
D7691 Test Method for Multielement Analysis of Crude Oils
Using Inductively Coupled Plasma Atomic Emission 4. Sampling
Spectrometry (ICP-AES) 4.1 Collection of a meaningful and representative sample is
D7740 Practice for Optimization, Calibration, and Valida- often the most critical step in an analytical procedure. In trace
tion of Atomic Absorption Spectrometry for Metal Analy- element analysis, in particular, extreme care must be taken to
sis of Petroleum Products and Lubricants

http://qstandard.org/
avoid contamination of the sample during the sampling step
2.2 Other Standards: and all subsequent analysis steps. By its very nature, crude oil
IP 570 Hydrogen Sulfide in Fuel Oils—Rapid Liquid Phase is typically non-homogenous, containing some percentages of
Extraction Method4 sediment and water. It also typically contains volatile light
ISO 8754 Petroleum Products, Determination of Sulfur ends, and finally, crude oil will often exhibit high pour point
Content, Energy Dispersive X-ray Fluorescence Spec- and high viscosity properties, due to its asphaltenes and
trometry5 paraffin wax content.
ISO 14596 Petroleum Products, Determination of Sulfur 4.1.1 The water and sediment component of the crude oil
Content, Wavelength Dispersive X-ray Fluorescence will tend to naturally separate and stratify in tanks, marine
Spectrometry5 vessel compartments, and in flowing pipelines.
UOP 163 Hydrogen Sulfide and Mercaptan Sulfur in Liquid 4.1.2 There are various types of containers that can be used
Hydrocarbons by Potentiometric Titration2 for storage of liquid hydrocarbon products. Not all of them are
UOP 938 Total Mercury and Mercury Species in Liquid suitable for crude oil storage. According to Practice D5854 for
Hydrocarbons2 tests of interest in elemental analysis area (salts, sulfur, and
trace metals) in crude oil, the containers employed may be
3. Significance and Use made of hard borosilicate glass, stainless steel, or epoxy-lined
steel and are considered satisfactory for immediate use, storage
3.1 This guide summarizes the test methods used in the up to six months or reuse. Less satisfactory are tin-plated
elemental analysis of crude oils. Additional information on the soldered steel, polytetrafluoroethylene propylene (PTFE), and
significance and use of the test methods quoted in this guide high-density linear polyethylene containers. See Table 1.
can be found under discussion of individual test methods in
Sections 8 through 15. 4.2 Three principal protocols are available for sampling of a
representative aliquot from a bulk sample: Practice D4057 for
3.2 Crude oils are highly complex hydrocarbons also con- manual sampling, Practice D4177 for automatic sampling, and
taining some organometallic compounds, inorganic sediment, Practice D5854 for mixing and handling of liquid samples.
and water. Nearly 600 individual hydrocarbons, over 200
separate sulfur compounds, and about 40 trace elements have 4.3 Crude oil to be sampled may be in static storage in a
tank, a marine vessel, or a pipeline. Stabilized crude oils
typically contain multiple phases, particulates, and volatiles.
4
Available from Energy Institute, 61 New Cavendish St., London, W1G 7AR,
U.K., http://www.energyinst.org.
5 6
Available from American National Standards Institute (ANSI), 25 W. 43rd St., The bold numbers in parentheses refer to the list of references at the end of this
4th Floor, New York, NY 10036, http://www.ansi.org. standard.

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 D8056 − 16
TABLE 1 Recommended Sample Containers for Crude Oil StorageA
Container Material For Immediate Use For Storage for 6 months For Reuse
Hard Borosilicate Glass Preferred Preferred Suitable
Stainless Steel Suitable Suitable Suitable
Epoxy-lined Steel Suitable Suitable Suitable
Tin-plated Soldered Steel Not recommended Not recommended Not recommended
Polytetrafluoroethylene Propylene (PTFE) Preferred Not recommended Suitable
High-density Linear Polyethylene (HDPE) Preferred Not recommended Not recommended
A
Excerpted from Practice D5854.

Decisions whether to separate the phases and analyze them 5.7 Determination of mercury in crude oil poses special
separately, or homogenize the whole sample need to be made problems both in sample collection and in measurement. These
prior to analysis. are discussed elsewhere in detail in Practice D7482, Test
4.4 If the sample does not readily flow at room temperature, Method D7622, and Test Method D7623.
heat it to a sufficiently high and safe temperature to ensure
adequate fluidity. Great care needs to be taken in heating the 6. Calibration
viscous sample prior to analysis. Changes in chemical 6.1 Depending upon the analysis being done, different
composition, loss of volatile elements, and so forth are causes calibration practices may have to be followed. A review of
for concern. calibration practices used in elemental analysis is given in
Guide D7578.
5. Sample Preparation
5.1 Often different test methods for specific determination 7. Analysis of Crude Oils
of elements require different sample preparation steps. Guide
D7455 reviews alternative techniques for sample preparation 7.1 A number of elemental analysis techniques have been
for elemental analysis. The means of sample preparation vary used in the analysis of crude oils. These include instrumental
from no sample preparation to simple sample dilution to techniques such as atomic absorption spectrometry (AAS),
inductively coupled plasma-atomic emission spectrometry

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extensive detailed procedures such as sample decomposition
depending on the measurement technique to be used for the (ICP-AES), inductively coupled plasma- mass spectrometry
final determination. (ICP-MS), isotope dilution mass spectrometry (IDMS), neu-
tron activation analysis (NAA), energy-dispersive X-ray fluo-
5.2 Among the test methods used for the elemental analysis
rescence (ED-XRF), and wavelength-dispersive X-ray fluores-
of crude oil, test methods such as XRF – Test Methods D2622
cence (WD-XRF). The highlights of these techniques and the
or D4294 for sulfur need no special preparation. However, they
examples of their utilization to elemental analysis of petroleum
may need dilution with a solvent if the sulfur levels are above
products and lubricants, and particularly to crude oils have
the scope of the test methods. Other non-XRF test methods that
been discussed in detail elsewhere (2, 6, 7).
do not need special sample treatment include Test Method
D3230 for salt by titration, and Test Methods D5291 for 7.2 Parameters that are usually determined for elemental
carbon-hydrogen-nitrogen by combustion. analysis are listed in Table 2 along with their scope and the
5.3 Some methods require sample dilution such as in atomic applicability of the test methods to crude oil assay. Several of
absorption spectrometry (AAS) Test Method D5863 B for the tests methods are not specifically designated for crude oil
nickel, vanadium, iron, and sodium; inductively coupled analysis but conventionally they are widely used for such
plasma-atomic emission spectrometry (ICP-AES) Test Method analyses in the industry.
D5708 for nickel, vanadium, and iron; and ICP-AES Test 7.2.1 Some of the ASTM tests listed in Table 2 have their
Method D7691 for multi-element analysis of crude oils. international counterparts listed in Table 3 (8).
5.4 Decomposition agents are employed to bring the desired 7.3 When performing several tests on a crude oil sample, it
parameter in aqueous solution for final measurement. Ex- is very important to ensure that the sequence of testing is
amples of these are Kjeldahl method for nitrogen: Test Method evaluated to minimize altering the properties of the remaining
D3228, acid decomposition of crude oil for vanadium: Test sample to be tested or retained. For crude oil samples, the
Method D1548, and AAS method for nickel, vanadium, iron, vapor pressure, H2S, or any other test in which retention of
and sodium: Test Method D5863 A. light ends is critical need to be analyzed first from the original
5.5 For volatile elements such as nitrogen or sulfur, com- sample container. For elemental analysis parameters, the se-
bustion trains using adsorbants have been used in Test Method quence of testing should be mercaptan sulfur, metals by AAS
D1552 for sulfur, and Test Methods D4629 and D5762 for or ICP-AES, nitrogen, salts, and sulfur by XRF, in that order.
nitrogen. 7.4 For several elemental tests, special precautions need to
5.6 Organic chloride in crude oil is determined by Test be taken in handling the crude oil samples during analysis.
Methods D4929 after elaborate pre-treatment of samples to Some of these are listed below in Table 4 excerpted from
separate organic chloride fraction from crude oil. Practice D4057.

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 D8056 − 16
TABLE 2 Scope and Applicability of Test Methods Used for Analysis in Crude Oils
NOTE 1—ICP-AES: Inductively Coupled Plasma Atomic Emission Spectrometry
CVAAS: Cold Vapor Atomic Absorption Spectrometry
ASTM
Analysis Measurement Technique Scope
Standard
A
D129 Sulfur Combustion – Gravimetry 0.09 % to 5.5 % by mass

A
D482 Ash Combustion 0.001 % to 0.180 % by mass

D1552A Sulfur Combustion – IR Detection >0.06 % by mass

D2622 Sulfur Wavelength Dispersive X-ray Fluorescence 3 mg/kg to 4.6 % by mass

A
D3227 Mercaptan Sulfur Potentiometric Titration 0.0003 % to 0.01 % by mass

D3228A Nitrogen Digestion – Titration 0.015 % to 2.0 % by mass

D3230 Salts Conductivity 0 mg ⁄kg to 500 mg/kg

D4294 Sulfur Energy Dispersive X-Ray Fluorescence 17 mg/kg to 4.6 % by mass

A
D4629 Nitrogen Oxidative Combustion and Chemiluminescence 0.3 mg/kg to 100 mg/kg
Detection

D4929 Organic Chloride Sodium Biphenyl Reduction and Potentiometry; or >1 mg/kg
Combustion and Microcoulometry

D5291A Carbon – Hydrogen-Nitrogen Combustion and Instrumental Detection <0.1 % to 2 % by mass Nitrogen

D5708 Nickel, Vanadium, Iron Acid Decomposition or Solvent Dilution + ICP- V: 50 mg/kg to 100 mg/kg;
AES Measurement Ni: 10 mg/kg to 100 mg/kg; and
Fe: 1 mg/kg to 10 mg/kg

D5762A Nitrogen Boat Inlet Combustion and Chemiluminescence 40 mg/kg to 10 000 mg/kg
Detection

D5863

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Nickel, Vanadium, Iron, Sodium Acid Decomposition or Solvent Dilution + AAS
Measurement
V: 50 mg/kg to 500 mg/kg;
Ni: 10 mg/kg to 100 mg/kg;
Fe: 3 mg/kg to 10 mg/kg; and
Na: 1 mg/kg to 20 mg/kg

D6470 Salts Solvent Extraction and Potentiometric Measure- 0.0005 % to 0.15 % mass ⁄mass
ment

D7621 Hydrogen Sulfide Dilution with base oil, extraction of H2S with air, 0 mg/kg to 150 mg/kg
and detection with H2S specific electrochemical
detector.

D7622 Mercury Combustion + CVAAS 5 ng/mL to 350 ng/mL

D7623 Mercury Combustion Gold Amalgamation + CVAAS 5 ng/mL to 400 ng/mL

D7691 Iron, Sulfur, Nickel, Vanadium Solvent Dilution + ICP-AES Measurement Fe: 1 mg/kg to 40 mg/kg;
Ni: 1 mg/kg to 100 mg/kg;
S: 400 mg/kg to 50 000 mg/kg; and
V: 1 mg/kg to 1000 mg/kg
A
Method scope does not include crude oils.

TABLE 3 International Equivalent Test Methods for Crude Oil AnalysisA

Analysis ASTM Institute of Petroleum/ International German Institute for Japanese Industrial
Energy Institute (IP) Standards Standardization (DIN) Standards (JIS)
Organization (ISO)
Sulfur by Bomb Method D129 61 51-577
Ash D482 4 6245 K 2272
Sulfur by WD-XRF D2622 14596 51-400T6 K 2541
Mercaptans D3227 342 3012 K 2276
Sulfur by ED-XRF D4294 336 8754
Nitrogen-Chemiluminescence D4629 379
Metals by AAS D5863 441
Hydrogen Sulfide D7621 570
A
From reference (8).

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 D8056 − 16
TABLE 4 Sample Handling for Elemental Analysis Tests for Crude Oils
Sample
Analysis Precautions to be Taken
Volume, mL
Mercaptan Sulfur (UOP 163); D3227 200 Minimize sample exposure to air.

Metals (D5863 B) 25 Prior to weighing stir the sample and then shake in its container. Employ adequate mixing and
sampling procedures for crude and heavy oils. Use paint mixer for mixing of crude oils. If the
sample does not readily flow at room temperature, heat the sample to a sufficiently high and
safe temperature to ensure adequate fluidity.

Nitrogen (D4629; D5762) 3 Test samples as soon as possible after taking from bulk supplies to prevent loss of nitrogen or
contamination due to exposure or contact with the sample container. If the test sample is not
used immediately, then thoroughly mix it in its container prior to taking a test specimen. Some
test samples require heating in order to thoroughly homogenize.

Salts (D3230) 10 The presence of water and sediment will influence the conductivity of the sample. The utmost
care shall be taken in obtaining homogenized representative samples. Samples of very viscous
materials may be warmed until they are reasonably fluid before they are sampled. However, no
sample shall be heated more than is necessary to lower the viscosity to a manageable level.

Salts (D6470) 50 Homogenize the sample within 15 min of drawing the test sample. Mix the sample at room tem-
perature (15 °C to 20 °C), or less in the laboratory sample container. Heat waxy samples, solid
at room temperature, to 3 °C above their pour point in order to facilitate sample withdrawal. See
Annex A1 of D6470 for mixer requirements and containers to be used.

Sulfur (D2622; D4294) 25 Be sure the sample is homogenous, and that there is no sediment or water present in the
sample aliquot taken.

8. Ash 9.2.1 Test Method D3227 is applicable to various fuels

8.1 Significance—Ash present in the crude oil results from containing from 0.0003 % to 0.01 % by mass mercaptan sulfur.
the presence of non-combustible extraneous solids such as Organic sulfur compounds such as sulfides, disulfides, and

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sediment, pipeline scales, rust and salt contamination from sea thiophene do not interfere. Elemental sulfur in amounts less
water. If the crude oil is used as a fuel, it is important to know than 0.0005 % by mass does not interfere. Hydrogen sulfide
its ash content because this could be related directly to will interfere if not removed as described in the test method. In
particulate emission. this test method, the hydrogen sulfide-free sample is dissolved
in an alcoholic sodium acetate titration solvent and titrated
8.2 Analysis—Ash in petroleum products is determined
potentiometrically with silver nitrate solution, using as an
using the Test Method D482. In this test, the sample contained
indicator the potential between a glass reference electrode and
in a suitable vessel is ignited and allowed to burn until only the
a silver/silver-sulfide indicating electrode. Under these
ash and carbon remain. The carbonaceous residue is reduced to
conditions, the mercaptan sulfur is precipitated as silver
an ash by heating in a muffle furnace at 775 °C, cooled, and
mercaptide and the end point of the titration is shown by a large
weighed.
change in cell potential.
8.3 Test Precision—Although crude oils were not specifi- 9.2.2 Test Method D7621 and its equivalent test method IP
cally analyzed by this test method to estimate precision, in 570 are automatic methods suitable for laboratory testing or
general, for petroleum products, the following precision is field use, and provides results in about 15 min. They can
expected. quantify hydrogen sulfide at a range from 0 mg ⁄kg to
Ash, percent by mass Repeatability Reproducibility 150 mg ⁄kg hydrogen sulfide in the liquid phase in a wide
0.001 to 0.079 0.003 0.005
0.080 to 0.180 0.007 0.024 variety of crude oils with an API ranging from 11.8 to 57.3, and
sulfur levels from 0.1 % to 6.7 %. In this test method, a sample
9. Mercaptans is introduced into a heated test vessel containing a diluent base
oil. Air is bubbled through the oil to extract the H2S gas. The
9.1 Significance—Hydrogen sulfide and mercaptans are
highly toxic and corrosive compounds that occur naturally in air with the extracted H2S is passed via a vapor phase processor
some crude oils. Thiols or mercaptans are considerably more to an H2S specific electrochemical detector enabling the H2S
prevalent in crude oil than H2S. They are the least stable sulfur content of the air to be quantitated.
compounds and many decompose on heating to form H2S (3). 9.2.2.1 The alternative procedure for crude oil is given in
Appendix X1 of Test Method D7621. The vapor phase proces-
9.2 Analysis—These compounds can be determined by non-
sor (Procedure A) is required for this analysis as vapor present
aqueous potentiometric titration with silver nitrate (Test
in the crude oil can damage the detector and chemical
Method D3227 and UOP 163). Although both methods are
interferences can be present.
similar, the ASTM method did not include crude oils in its
scope. IP method 570 and its equivalent Test Method D7621 9.3 Test Precision—Following precision was obtained from
can determine amount of hydrogen sulfide in crude oils. interlaboratory studies.

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 D8056 − 16
9.3.1 Precision of Test Method D3227 has been found to be 10.2.2 Test Method D7623 and UOP 938—A crude oil
as follows. This study did not include crude oils in the matrix. sample is heated to dryness in an oxygen atmosphere in the
Repeatability 0.00007 + 0.027 X instrument, and then thermally (at about 700 °C) and then
Reproducibility 0.0031 + 0.042 X chemically decomposed. The decomposition products are car-
Where X is the average mercaptan sulfur, percent by mass.
ried by flowing treated air to the catalytic section of the furnace
(at about 850 °C), where oxidation is completed. The decom-
9.3.2 Only repeatability estimate of Test Method D7621 is position products are carried to a gold amalgamator that
available. In one study a single laboratory analyzed 21 samples selectively traps mercury. After the system is flushed with
of crude oil ranging in their H2S levels from 0 mg ⁄kg to oxygen to remove any remaining decomposition products other
150 mg ⁄kg and found a repeatability of 12 mg ⁄kg. A similar than mercury, the amalgamator is rapidly heated to about
analysis of 12 lowest H2S level samples ranging in the 600 °C, releasing mercury vapor. Flowing oxygen carries the
concentration from 0 mg ⁄kg to 50 mg ⁄kg found a repeatability mercury vapor through absorbance cells positioned in the light
of 5 mg ⁄kg. path of single wavelength cold vapor atomic absorption spec-
trophotometer. Absorbance peak height or peak area, as a
10. Mercury function of mercury concentration, is measured at 253.65 nm.
10.1 Significance—Mercury has been designated by Envi- 10.2.2.1 An Appendix to UOP 938 Test Method also con-
ronmental Protection Agency (EPA) and many state agencies tains a procedure that can be used to differentiate between
as a hazardous material that can cause central nervous system, elemental mercury, organic non-ionic mercury, and ionic (in-
kidney, and liver damage. Mercury or its vapors may be organic and organic) mercury species.
hazardous to health and corrosive to material. Mercury can 10.3 Test Precision—Based on an interlaboratory study
occur in crude oil as volatile, dissolved, and particulate (RR:D02-1692)7 following precision was obtained. Reproduc-
(suspended) species—all of which differ considerably in their ibility limit is not yet available.
chemical structure and chemical behavior. Elemental mercury Test Method Scope Repeatability Reproducibility
has been found in condensed in cooled regions in refinery D7622 5 ng ⁄mL to 0.7147 X0.6 NA
distillation towers and in cryogenic heat exchangers that 350 ng/mL
D7623 5 ng/mL to 0.4396 NA
liquefy petroleum gases. Mercury can be present in various 400 ng/mL X0.5864
distillation fractions across a broad boiling range (1, 3).

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Where X is the average mercury concentration in ng/mL.
10.1.1 Mercury is present at low ppm to ppb levels in crude
oils. Giles et al have reported mercury in the range from 11. Nitrogen
0.02 ng ⁄g to 10 ng ⁄g (1, 3). Others also have reported mercury
in the less than a ppb level in crude oil (9, 10). Mercury 11.1 Significance—Nitrogen is an important element for
speciation is predominantly Hg(0) present as a mixture of determining in crude oil. Numerous nitrogenous compounds
dissolved Hg(0) atoms, adsorbed Hg(0) on particulates and are present in crude oils. Many problems are caused by their
suspended droplets of metallic mercury (11). Practice D7482 presence in refining and product quality. As a group even their
should be used for guidance for sampling, storage, and trace quantities present in feedstocks can contaminate refinery
handling of hydrocarbons for mercury analysis. catalysts. Nitrogen compounds can also contribute to refined
product instability, are responsible for formation and precipi-
10.2 Analysis—Given the ultra-trace levels of mercury pres- tation of gum, and contribute to environmental pollution when
ent in crude oil, there are only limited analytical techniques fuels are burned by emission of nitrogen oxides (NOx) (3).
available for such analysis. Basically the methods available are
a variation on the basic cold vapor atomic absorption spec- 11.2 Analysis—There are four principle test methods for the
trometry technique. determination of nitrogen in crude oils: Test Methods D3228,
D4629, D5291, and D5762. None of them are specifically
10.2.1 Test Method D7622—The crude oil sample placed in
meant for analysis of crude oils. However, they are commonly
a sample boat is inserted in the first chamber of an atomizer
used when necessary for crude oils.
where the sample is heated at 300 °C to 500 °C. The mercury
11.2.1 Kjeldahl Method—Test Method D3228 is not often
compounds are evaporated and partially dissociated forming
used in analysis of crude oils, and uses sample digestion in a
elemental mercury vapor. Mercury and all decomposition
mixture of concentrated sulfuric acid, potassium sulfate, mer-
products are carried to a second atomizer chamber heated to
curic oxide, and copper sulfate to convert nitrogen species into
about 700 °C to 750 °C. Mercury compounds are totally
inorganic nitrate compounds. After digestion, sodium sulfide is
dissociated, and the organic matrix of the sample is burnt out.
added to precipitate the mercury as mercuric sulfide, and the
Continuously flowing air carries mercury and other combustion
mixture is made alkaline with NaOH. Nitrogen, now in the
products through absorbance analytical cell heated up to
form of ammonia, is distilled into a boric acid solution. The
750 °C positioned in the light path of double-wave cold vapor
ammonia is titrated with standard sulfuric acid using methyl
Zeeman atomic absorption spectrometer. The mercury reso-
purple as an indicator. Kjeldahl method may not be applicable
nance line at 253.65 nm is split to several components, one of
to certain materials containing N-O or N-N linkage.
those falling within the mercury absorbance line profile and
another one lying outside. Difference between the intensities of
these two lines is proportional to the number of mercury atoms 7
Supporting data have been filed at ASTM International Headquarters and may
in the analytical cell. be obtained by contacting ASTM Customer Service at [email protected].

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 D8056 − 16
11.2.2 Syringe/inlet Oxidative Combustion and Chemilumi- 11.3 Test Precision—Based on various interlaboratory stud-
nescence Detection Method—Test Method D4629 can analyze ies following precisions were found for the above test methods
total nitrogen found in liquid hydrocarbons boiling in the range for nitrogen (Table 5).
of approximately 50 to 400°C, with viscosities between ap-
proximately 0.2 and 10 cSt at room temperature. This method 12. Organic Chloride
is applicable to naphthas, distillates, and oils containing
12.1 Significance—Organic chlorides do not occur naturally
0.3 mg ⁄kg to 100 mg/kg of total nitrogen. In this test method,
in crude oil. If present they result from contamination in some
a sample of liquid hydrocarbon is introduced either by syringe
manner, such as disposal of chlorinated solvent in many
or boat inlet system, into a stream of inert gas such as helium
dewaxing pipelines or other equipment operations. Uncontami-
or argon. The sample is vaporized and carried to a high
nated crude oil will not contain any detectable organic
temperature zone where oxygen is introduced and the organi-
chloride, and most refineries can handle very small amounts
cally bound nitrogen is converted to nitric oxide (NO). The NO
without deleterious effects. Most trade contracts specify that no
contacts ozone, and is converted to excited nitrogen dioxide
organic chloride be present in the crude oil. Several pipeline
(NO2). The light emitted as the excited NO2 decays is detected
organizations have set specification limits at <1 mg/kg organic
by a photomultiplier tube and the resulting signal is a measure
chlorides in the whole crude oil, and <5 mg/kg in the light
of the nitrogen contained in the sample.
naphtha, on the basis of the naphtha fraction being 20 % of the
11.2.3 Instrumental Determination of Carbon-Hydrogen-
original sample (3).
Nitrogen—Test Methods D5291 consists of four separate
12.1.1 Organic chloride species are potentially damaging to
procedures for simultaneous determination of carbon,
refinery process. Hydrochloric acid can be produced in hy-
hydrogen, and nitrogen in petroleum products including crude
drotreating or reforming reactors, and the acid accumulates in
oil and lubricants. Each procedure is dedicated to a separate
the condensing regions of the refinery. Unexpected concentra-
instrument type available. Basically, in each type of
tions of organic chlorides can be effectively neutralized and
instrument, a sample is combusted at an elevated temperature
damage can result (3).
in an atmosphere temporarily enriched in purified oxygen to
convert the constituents to carbon dioxide, hydrogen halides, 12.2 Analysis—In Test Methods D4929, crude oil distilla-
water vapor, elemental nitrogen and nitrogen oxides, and sulfur tion is performed to obtain the naphtha cut at 204 °C. The
oxides. Different absorbers are used in each instrument to naphtha cut is washed with caustic, repeatedly when necessary,
remove undesirable products and separate the desired constitu- until all hydrogen sulfide is removed. The naphtha cut, free of

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ents. Eventually, after the gaseous separation, the nitrogen
species is measured using thermal conductivity cell or an IR
detector.
hydrogen sulfide, is then washed with water, repeatedly, when
necessary, to remove inorganic halides (chlorides). This is
followed by two alternative test methods for the determination
of organic chloride in the washed naphtha fraction as follows.
11.2.4 Boat-inlet Combustion and Chemiluminescence De-
tection Method—Test Method D5762 can be used for deter- 12.2.1 Procedure A—The washed naphtha fraction is treated
mining nitrogen in liquid hydrocarbons, including petroleum with sodium biphenyl reagent in toluene. The free radical
process streams and lubricating oils in the nitrogen concentra- nature of this reagent promotes very rapid conversion of the
tion range from 40 µg ⁄g to 10 000 µg ⁄g. In this test method, a organic halogen to inorganic halide. The excess reagent is
hydrocarbon sample is placed in a sample boat at room decomposed, the mixture acidified, and the phases separated.
temperature. The sample boat is advanced into a high- The aqueous phase is evaporated to a small volume, acetone is
temperature combustion tube where the nitrogen is oxidized to added and the solution is titrated potentiometrically.
nitric oxide (NO) in an oxygen atmosphere. The NO contacts 12.2.2 Procedure B—The washed naphtha fraction is com-
ozone and is converted to excited nitrogen dioxide (NO2). The busted in a flowing tube at about 800 °C in a flow of oxygen
light emitted as the excited NO2 decays is detected by a plus an inert gas. The chlorine is converted to chloride and
photomultiplier tube, and the resulting signal is a measure of oxychlorides which then flow into a titration cell where they
the nitrogen contained in the sample. are titrated with silver nitrate solution coulometrically.

TABLE 5 Precision of Test Methods for Determination of Nitrogen in Crude Oils

NOTE 1—Where X is the average of the two test results.
NA: Not available
Test Method Matrix Repeatability Reproducibility ASTM Research ReportA
D3228 Lubricating Oils 0.01 % by mass 0.02 % by mass NA
Fuel Oils 0.066 x m0.5 0.190 x m0.5 NA

D4629 Liquid Hydrocarbons 0.1825 X0.5149 0.8094 X0.5149 RR:D02-1199 and RR:D02-1527

D5291 Petroleum Products 0.1670 0.4456 RR:D02-1289 and RR:D02-1679

0.006897(X + 3) 0.02967 (X + 3)

D5762 Liquid Hydrocarbons 0.087 X 0.266 X RR:D02-1370 and RR:D02-1507

A
Supporting data have been filed at ASTM International Headquarters and may be obtained by contacting ASTM Customer Service at [email protected].

7
 D8056 − 16
12.3 Test Precision—Following precision of the two proce- water in an electrically heated extraction apparatus. A portion
dures in Test Methods D4929 was obtained based on an of the aqueous extract is analyzed for total halides by poten-
interlaboratory study (RR:D02-1293).7 tiometric titration.
Test Method A B 13.2.3 Results by Test Method D3230 are expressed in units
Repeatability 0.32 (X + 0.33)0.644 1.01 (X – 0.17)0.467 of mg/kg. Alternatively, they can also be reported in units of
Reproducibility 0.7 (X + 0.33)0.644 1.32 (X – 0.17)0.467 g/m3 or as lb/1000 bbl (a common industry reporting practice),
if so required. Results by Test Method D6470 are reported as
13. Salts mass %. The result units can be converted by formula given
13.1 Significance—A knowledge of the salt content of crude below:
oil is important in deciding whether or not the crude oil needs Salt, mg/kg 5 ~ 1000 X ! ⁄d or (3)
desalting. The efficiency of the desalter process can also be
Salt, mg/kg 5 2.853 Y⁄d (4)
evaluated. Excessive chloride left in the crude oil frequently
results in high corrosion rates in refining units, and also has where:
detrimental effects on catalysts used in these units. The salt X = measured salt concentration in g/m3,
content of crude oils can be highly variable, and results Y = measured salt concentration in PTB, and
principally from the production practices used in the field and D = specimen density at 15 °C in kg/m3.
to a lesser extent from its handling by tankers abroad, which 13.3 Test Method Precision—Based on interlaboratory stud-
transport crude oil to the terminals. The bulk of the salt present ies following precisions have been obtained for the above two
will be dissolved in co-existing free water and can be removed test methods (Table 6).
in desalters. But small amounts of salt may be dissolved in the 13.3.1 Test Method Bias—Since salt content of crude oil is
crude oil itself (3). defined only in terms of these tests, and since there are no
13.1.1 Salt in crude oil may be deleterious in several ways. standard reference materials available for such analysis, no
Even in small concentrations, salts will accumulate in stills, statement regarding bias of these test methods can be made.
heaters, and exchangers, leading to fouling that leads to 13.3.2 In one study (RR:D02-1470)7 the samples were near
extensive cleanup. During flash vaporization of crude oils, desalted crudes, spiked with known quantities of salt (as sea
certain metallic salts can be hydrolyzed to hydrochloric acid water and formation water), bias might be defined as percent
according to the following equations: recovery of added halides. Over the range from 5 g ⁄m3 to 500

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2NaCl1H 2 O→2HCl1Na 2 O (1) g/m3 (1.5 PTB to 150 PTB) salt added, the recovery proved to
be approximately constant and averaged 93 % for D3230 test
MgCl 2 1H 2 O→2HCl1MgO (2)
method. In a similar study (RR:D02-1458),7 over the range
13.1.2 The hydrochloric acid evolved is extremely 0.0005 % to 0.0400 % by mass salt added, the recovery proved
corrosive, necessitating the injection of a basic compound such to be constant and averaged 97 % for D6470 test method. Over
as ammonia into the overhead lines to minimize damage (3). the range 0.0400 to 0.1500, the recovery proved to be a
function of concentration and gradually decreased from 97 %
13.2 Analysis—There are two test methods available for this at 0.04 % by mass to 88 % at the 0.15 % by mass level.
analysis: D3230 Salts in Crude Oil (Electrometric Method) and
D6470 Salts in Crude Oil (Potentiometric Method). Samples of 14. Sulfur
crude oil contain water and sediment and are inhomogenous by 14.1 Significance—Perhaps the largest amount of data col-
nature. Homogenization of crude oil is an important step in lected in the analysis of crude oils is for sulfur. This is
either of these two test procedures. Samples of very viscous
crude oils may have to be warmed until they are reasonably TABLE 6 Precision of Test Methods for Salt Content of
fluid before they are sampled. However, no samples shall be Crude Oils
heated more than necessary to lower the viscosity to a NOTE 1—Where:
manageable level. X = the average of two test results in mg/kg (for D3230) and in mass
% (for D6470)
13.2.1 Test Method D3230—This test method measures Y = the average of two test results in lb/1000 bbl (PTB)
conductivity in the crude oil due to the presence of common
Parameter D3230 D6470
chlorides, such as sodium, calcium, and magnesium. Other
Scope 0 mg ⁄kg to 500 mg/kg or 0.0005 % to 0.15 %
conductivity materials may also be present in the crude oil. A 0 lb ⁄1000 bbl to 150 lb/1000 bbl m ⁄m
homogenized test specimen of crude oil is dissolved in a mixed
alcohol solvent and placed in a test cell consisting of a beaker Repeatability 0.3401 X0.75 mg/kg or 0.0243 X0.612 % by
0.2531 Y0.75 lb/1000 bbl mass
and a set of electrodes. A voltage is impressed on the
electrodes, and the resulting current flow is measured. The Reproducibility 2.7803 X0.75 mg/kg or 0.0477 X0.612 % by
2.069 Y0.75 lb/1000 bbl mass
chloride (salt) content is obtained by reference to a calibration
curve of current versus chloride concentration of known ASTM Re- RR:D02-1470 RR:D02-1458
mixtures. search Re-
portA
13.2.2 Test Method D6470—After homogenizing crude oil A
Supporting data have been filed at ASTM International Headquarters and may be
with a mixer, a weighed aliquot is dissolved in xylene at 65°C obtained by contacting ASTM Customer Service at [email protected].
and extracted with specified volumes of alcohol, acetone, and

8
 D8056 − 16
appropriate given the importance of sulfur chemistry and its ences. In general, petroleum materials with compositions that
effect on utilizing crude oil in the industry. The sulfur content vary from white oils can be analyzed with standards made from
of crude oils can vary from less than 0.1 % by mass to over 5 % base materials that are of the same or similar composition.
by mass. Chapter 23 in Ref (2), Chapter 7 in Ref (6), and 14.2.4 Test Method D4294—This test method employing
Chapter 5 in Ref (7) have covered various aspects of occur- energy-dispersive X-ray fluorescence (ED-XRF) technique is
rence and analysis of sulfur in petroleum products, fuels, and also widely used in the oil industry for determination of sulfur.
lubricants. Reservations similar to those described in 14.2.3 and 14.2.3.2
14.1.1 Sulfur compounds are some of the most egregious regarding test interferences apply to this test method also.
non-hydrocarbon materials present in crude oils. They contrib- However, the D4294 instrumentation is far less expensive than
ute to corrosion of refinery equipment, poisoning of catalysts, the one required for Test Method D2622.
cause corrosiveness in refined products, and contribute to 14.2.4.1 In this test method, a sample is placed in the beam
environmental pollution through emission of sulfur oxides emitted from an X-ray tube. The resultant excited characteristic
from combustion of fuel products (1, 3). X radiation is measured, and the accumulated count is com-
pared with counts from previously prepared calibration
14.2 Analysis—As to be expected, a large number of test
samples to obtain the sulfur concentration. A typical analysis
methods for sulfur determination in petroleum products and
time is 1 min to 5 min per sample. High-purity di-n-butyl
lubricants have been issued by ASTM (7, 8). Many of the
sulfide of known sulfur content is used as the calibrant
earlier test methods such as D129 or D1552 have been
material. A minimum of three groups of calibration samples are
superseded by modern instrumental test methods such as
required to span the concentration range of sulfur from 0.0 %
D2622, or D4294 based on X-ray fluorescence technology.
to 5.0 % by mass. See Practice D7343 for protocol used for
Protocol for using XRF analyzers has been described in Guide
XRF analysis of petroleum products.
D7343.
14.2.5 In both above XRF test methods, interferences from
14.2.1 Test Method D129—This is a much older test method
other inorganic elements present in crude oil need to be taken
involving combustion of a sample in an oxidation bomb with
into consideration. Modern built-in software often can take
subsequent gravimetric determination of sulfur as barium
care of required corrections. Sediment, water and waxes
sulfate. This is not as accurate a method as Test Method D1552,
commonly present in crude oil samples can settle onto the
partially because of interference from the sediment inherently
Mylar™ film used for sealing the test cup and interfere in
present in crude oil.
sulfur determination. Before analysis, water and particulates

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14.2.2 Test Method D1552—This test method uses combus- should be removed from the samples by centrifuging or
tion of the sample in oxygen to convert the sulfur to sulfur settling, but care must be taken that the sample integrity is not
dioxide, which is collected and subsequently detected by compromised (1, 3).
non-dispersive infrared (IR) spectroscopy.
14.2.3 Test Method D2622—This test method is widely used 14.3 Test Method Precision—Through a number of inter-
in the industry for analysis of a wide variety of petroleum and laboratory studies following precisions have been established
lubricant products including crude oils. A fundamental assump- for the above four sulfur test methods (Tables 7 and 8).
tion of this test method is that the standard and sample matrices 14.3.1 Following precision is given for analysis of petro-
are well matched, or that the matrix differences are accounted leum products by Test Methods D129 and D1552. It is not clear
for. Matrix mismatch can be caused by C/H ratio differences whether crude oils were included in this estimation (RR:D02-
between samples and standards or by the presence of other 12787 and RR:D02-1231,7 respectively).
interfering heteroatoms or species. However, as far as crude 14.3.2 The bias in using Test Methods D2622 and D4294
oils are concerned, none of the expected interfering elements were studied using NIST crude oil standard reference materials
are present in them. A typical analysis time is 1 min to 2 min (SRMs) and is shown in Table 9. No bias was evident for SRM
per sample. 2721 for either of the two test methods as shown in Table 9.
14.2.3.1 In this test method employing wavelength disper- But a small bias was found for SRM 2722, perhaps because of
sive X-ray fluorescence (WD-XRF), a sample is placed in the the smaller amount of sulfur present in it.
X-ray beam, and the peak intensity of the sulfur K α line at
TABLE 7 Precision of D129 and D1552 Test Methods for Sulfur
0.5373 nm is measured. The background intensity, measured at
a recommended wavelength of 0.5190 nm for chromium or Sulfur, Repeatability Reproducibility
mass % D129A D1552 D129A D1552
scandium target tubes (or 0.5437 nm for a rhodium target tube)
is subtracted from the peak intensity. The resultant net counting 0.1 to 0.5 0.04 0.04 0.05 0.13
0.5 to 1.0 0.06 0.07 0.09 0.21
rate is then compared to a previously prepared calibration 1.0 to 1.5 0.08 0.15
curve or equation to obtain the concentration of sulfur in 1.0 to 2.0 0.09 0.27
milligrams per kilogram or mass percent. Usually high-purity 1.5 to 2.0 0.12 0.25
2.0 to 3.0 0.12 0.38
di-n-butyl sulfide of known sulfur content is used as a 3.0 to 4.0 0.13 0.44
calibrant. 2.0 to 5.0 0.18 0.27
4.0 to 5.0 0.16 0.49
14.2.3.2 When this test method is applied to petroleum
A
materials with matrices significantly different from the white Equivalent IP method 61 gives a repeatability of 0.016 X + 0.06 and a
reproducibility of 0.037 X + 0.13, where X is the mean of duplicate analysis, in
oil calibration material specified in this test method, results percent mass.
should be interpreted with caution with regards to interfer-

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TABLE 8 Precision of Sulfur Test Methods for Crude Oil Analysis by XRF
NOTE 1—Where X is the sulfur concentration in mg/kg.
Test Method Concentration Range PLOQ (per D6259) Repeatability, mg/kg Reproducibility, mg/kg ASTM Research ReportA
D2622 3 mg/kg – 4.6 mass % 3 mg/kg 0.1462 X0.8015 0.4273 X0.8015 RR:D02-1622
D4294 17 mg/kg – 4.6 mass % 16.0 mg/kg 0.4347 X0.6446 1.9182 X0.6446 RR:D02-1635
A
Supporting data have been filed at ASTM International Headquarters and may be obtained by contacting ASTM Customer Service at [email protected].

TABLE 9 Analysis of NIST Crude Oil SRMs for Sulfur 15.2.2 Test Method D5863—This test method also has two
NIST SRM 2721 NIST SRM 2722 procedures. Method A uses flame AAS after a sample is
Parameter
D2622 D4294 D2622 D4294 decomposed with concentrated sulfuric acid for the determina-
NIST Sulfur Value, mg/kg 15 832 15 832 2104 2104 tion of total nickel, vanadium, and iron. Method B uses a
Average Measured, mg/kg 15 884 16 118 2054 2082 sample diluted in an organic solvent for measurement of
Measured Reproducibility, 1170 988.4 181 264.2
mg/kg nickel, vanadium, and sodium. The measurement technique in
Measured Bias, mg/kg 54 +288 –49 –21 both procedures is flame AAS.
Relative Measured Bias, % 0.34 1.82 –2.33 –1 15.2.3 Test Method D7691—This test method utilizes ten-
fold dilution of a thoroughly homogenized crude oil sample
with mixed xylenes, kerosene, or other suitable solvent. An
internal standard is added to the solutions to compensate for
15. Trace Metals variations in test specimen introduction efficiency. The ele-
15.1 Significance—Besides sulfur and nitrogen, there are ments of interest are measured by ICP-AES. This work has
several inorganic elements present in crude oils at varying been published in reference (12). Besides the four elements for
levels. As many as 45 elements have been reported to be which precision is given in Table 10 for this test method, a
present in crude oils. Their presence can have adverse effect on number of other trace elements were looked for in the analysis
petroleum refining such as catalyst poisoning in the refinery, protocol. This included aluminum, boron, barium, calcium,
product quality and the environment. Elements such as iron, chromium, copper, potassium, magnesium, manganese,
arsenic, and lead are catalyst poisons. Vanadium compounds molybdenum, sodium, phosphorus, lead, silicon, and zinc.

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can cause refractory damage in furnaces, and sodium com- Although ICP-AES technique is capable of detecting all of
pounds have been found to cause superficial fusion on fire these elements, in the suite of crude oils analyzed in this study,
brick (1, 3). Some organometallic compounds are volatile none of them were detected.
which can lead to the contamination of distillate fractions, and 15.2.3.1 Test Methods D5708 and D5863 determine the
a reduction in their stability or malfunctions of equipment elements either by straight organic solvent dilution or alterna-
when they are combusted. It is widely accepted that trace tively by first decomposing the matrix with concentrated
elements are present in crude oil as porphyrins and non- sulfuric acid. It has been speculated that since organic solvent
porphyrin complexes. dilution may not dissolve particulates in the crude oil, this
technique may give lower results and may not account for the
15.2 Analysis—The most commonly analyzed trace ele- total metal contents of elements. However, based on data
ments in crude oils are nickel, vanadium, iron, sodium, and obtained in ASTM Proficiency Testing Programs on crude oils,
mercury. See Section 10 regarding discussion about mercury it is not clear that organic solvent dilution techniques would
analysis. Two principal test methods used for multielement necessarily give lower results than those obtained using acid
analysis of crude oil are Test Methods D5708, D5863, and decomposition techniques (2, 12).
D7691. While Test Method D5863 uses atomic absorption
spectrometry (AAS) for measurements, the other two Test 15.3 Test Method Precision—The precisions obtained for
Methods D5708 and D7691 use inductively coupled plasma these three atomic spectroscopic test methods for metal analy-
atomic emission spectrometry (ICP-AES). Both are widely sis are given in Table 10.
used atomic spectrometric measurement techniques in the oil 16. Quality Control
industry, and have been discussed in Practices D7260 (for
ICP-AES) and D7740 (for AAS). 16.1 It is recommended that each laboratory establish a
program to ensure that the measurement system described in
ASTM
Test these test methods are in statistical control. One part of such a
Technique Analytes Research
Method
Report program might be the regular use of control charting of quality
D5708 ICP-AES Ni, V, and Fe RR:D02-1351
D5863 AAS Ni, V, Fe, and Na RR:D02-1351
control samples. It is recommended that at least one type of
D7691 ICP-AES Ni, V, Fe, and S RR:D02-1761 quality control (QC) sample be analyzed that is representative
15.2.1 Test Method D5708—There are two procedures in of the typical laboratory samples. Further guidance on quality
this method. Method A analyzes a sample dissolved in an control charting and their interpretation can be found in
organic solvent and uses oil-soluble metals for calibration. In Practices D6299 and D6792.
Method B the sample is decomposed with concentrated sulfuric 16.2 Stable petroleum product samples should be used as
acid before measurement in an aqueous solution. The measure- representative quality control samples. Suitable QC samples
ment technique in both procedures is ICP-AES. can be prepared by combining retains of typical samples of

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 D8056 − 16
TABLE 10 Precision of Atomic Spectroscopic Test Methods for Metal Analysis of Crude Oils
NOTE 1—Where X is the mean concentration in mg/kg.
Test Method Element Concentration Range, mg/kg Repeatability Reproducibility
D5708 A Vanadium 50 – 500 0.07 X0.88 0.12 X1.1
D5708 B 0.02 X1.1 0.10 X1.1

D5708 A Nickel 10 – 100 0.01 X1.3 0.41 X0.78

D5708 B 0.02 X1.2 0.05 X1.3

D5708 A Iron 1 – 10 0.22 X0.30 0.68 X0.35

D5708 B 0.23 X0.67 0.91 X0.51

D5863 A Vanadium 50 – 500 1.1 X0.50 0.33 X0.90

D5863 B 0.13 X0.92 1.2 X0.80

D5863 A Nickel 10 – 100 0.20 X0.65 1.3 X0.53

D5863 B 0.005 X1.4 0.06 X1.2

D5863 A Iron 3 – 10 0.98 1.45 X0.45

D5863 B Sodium 1 – 20 0.12 X 0.69 X

0.9145
D7691 Iron 1 – 40 0.1885 X 0.5649 X0.9145
Nickel 1 – 100 0.1764 X1.0168 1.1389 X0.7085
Sulfur 400 – 50 000 0.01971 X1.1606 0.06360 X1.1606
Vanadium 1 – 1000 0.0392 (X+0.7485)0.8668 0.8628 (X+0.7485)0.8668

known sulfur concentration, if they are stable. Retains of wide participating in them. The crosschecks are conducted
D02.92 Proficiency Testing Programs of crude oil are available every March, July, and November. Among several analyses
at a small cost from ASTM Proficiency Testing Program (PTP) conducted in this program include elemental analysis Test
office. They can be utilized in such a QC program in the Methods D5708 and D5863 for vanadium, nickel, and iron,
laboratory. Test Methods D4629 and D5762 for nitrogen, Test Methods

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16.3 Additionally, the QC program can also use Standard
Reference Materials available from National Institute of Sci-
ence and Technology (NIST). Some of the crude oil materials
D3230 and D6470 for salt, and Test Methods D2622 and
D4294 for sulfur. Protocol for conducting PTP crosschecks is
described elsewhere (13) and interpreting the PTP results is
available from NIST are listed in Table 11. See the NIST described in Guide D7372 and in Ref (14).
website for detailed information about the analysis and avail- 17.2 Examples of crude oil PTP results from 2015 cycle are
ability of the SRMs.8 given in Table 12. Generally, alternative test methods for the
16.3.1 NIST certifies sulfur concentration in their SRMs same parameter give equivalent results, for example, sulfur by
using WD-XRF method ISO 14596 with zirconium as internal Test Methods D2622 or D4294, nitrogen by Test Methods
standard and isotope dilution—inductively coupled plasma D4629 or D5762, iron, nickel, and vanadium by Test Methods
mass spectrometry after microwave digestion of the sample. D5798 A, D5708 B, D5863 A, or D5863 B. See Table 13 for
a comparison of Test Performance Index (TPIIndustry) for these
17. Proficiency Testing Programs
analyses. TPI is an approximate measure of a laboratory’s
17.1 For last several years, D02.92 has conducted a large testing capability defined by a calculated value of ratio of
number of proficiency testing programs (PTP) for a number of calculated ASTM test method reproducibility to site precision.
petroleum products and lubricants. Crude oil PTPs were TPIIndustry calculation is based on the ratio of the test method
initiated in 2000 and currently have 294 laboratories world- reproducibility to the robust reproducibility of the program
data. These calculation routines are described in Guides D6792
8
and D7372. Usually TPI values less than 1 may be cause for
Available from National Institute of Standards and Technology (NIST), 100
Bureau Drive, Stop 1070, Gaithersburg, MD 20899-1070, http://www.nist.gov. concern regarding the performance of the laboratories involved

TABLE 11 Crude Oils Standard Reference Materials from NIST

SRM # Description Sulfur Concentration Other Elements
2721 Light sour crude oil 1.5832 % ± 0.0044 % by mass Mercury: 0.0417 µg ⁄kg ± 0.0057 µg/kg
Carbon: 84.6 % by mass
Hydrogen : 11.8 % by mass

2722 Heavy sweet crude oil 0.21037 % ± 0.00084 % by Mercury: 0.129 µg/kg ± 0.013 µg/kg
mass Carbon: 85.9 % by mass
Hydrogen: 11.9 % by mass

RM 8505 Crude Oil Vanadium: 390 mg/kg ± 10 mg/kg

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TABLE 12 Crude Oil Proficiency Testing Program Results for 2015
NOTE 1—Results are expressed as Robust Mean ± Robust Standard Deviation (Valid Results).
NA: Not available.
Analysis Test Method CO 1503 CO 1507 CO 1511
Sulfur, % by mass D2622 0.969 ± 0.031 (34) 3.715 ± 0.118 (32) 0.579 ± 0.028 (34)
D4294 0.988 ± 0.024 (167) 3.837 ± 0.098 (168) 0.601 ± 0.020(162)

Salts, mg/kg D3230 6.98 ± 2.14 (94) 20.971 ± 9.166 (94) 82.99 ± 48.8 (83)
D6470 NA (4) NA (4) 364.1 ± 51.4 (7)

Nitrogen, mg/kg D4629 1391.8 ± 328.6 (34) 2542.1 ± 953.0 (38) 1697.8 ± 575.3 (42)
D5762 1563.6 ± 238.0 (54) 3053.0 ± 576.2 (54) 1947.1 ± 313.1 (58)

Chloride ,mg/kg D4929 B 0.69 ± 0.68 (8) 0.20 ± 0.17 (11) 0.29 ± 0.32 (12)

Iron, mg/kg D5708 A 0.749 ± 0.158 (39) 0.843 ± 0.338 (37) 9.82 ± 4.37 (51)
D5708 B 1.166 ± 0.474 (39) 1.672 ± 0.427 (32) 16.83 ± 6.40 (40)
D5863 A 1.72 ± 0.81 (21) 2.24 ± 0.81 (17) 15.82 ± 6.47 (19)

Nickel, mg/kg D5708 A 11.29 ± 1.56 (44) 56.46 ± 5.22 (48) 9.84 ± 1.30 (51)
D5708 B 10.515 ± 1.311 (42) 56.245 ± 4.622 (39) 7.59 ± 1.93 (40)
D5863 A 11.23 ± 1.43 (26) 57.75 ± 7.03 (18) 7.87 ± 1.21 (16)
D5863 B 12.12 ± 1.72 (20) 60.97 ± (7.78) (17) 9.61 ± 1.93 (20)

Vanadium,mg/kg D5708 A 26.73 ± 2.67 (47) 306.70 ± 43.50 (50) 15.53 ± 1.81 (51)
D5708 B 24.692 ± 2.235 (42) 301.005 ± 19.281 (37) 13.94 ± 1.43 (38)
D5863 A 22.514 ± 3.318 (24) 284.8 ± 40.115 (19) 13.77 ± 1.04 (13)
D5863 B 26.92 ± 3.64 (22) 295.94 ± 21.39 (18) 16.72 ± 4.10 (10)

TABLE 13 Test Performance Indices for 2015 Crude Oil PTP Analyses

NOTE 1—NA: Not Available.

Analysis Test Method CO 1503 CO 1507 CO 1511

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Sulfur D2622 0.78 0.60 0.56
D4294 1.00 0.64 0.95

Salts D3230 1.50 0.80 0.42

D6470 NA NA 0.44

Nitrogen D4629 27.1A 57.6A NA

D5762 0.63 0.51 0.60

Chloride D4929 B 0.53 0.55 0.55

Iron D5708 A 0.72 1.46 0.12

D5708 B 0.75 1.00 NA
D5863 A 1.21 1.08 NA

Nickel D5708 A 0.63 0.66 NA

D5708 B 0.29 0.74 NA
D5863 A 1.18 0.57 NA
D5863 B 0.25 0.39 NA

Vanadium D5708 A 1.66 0.54 NA

D5708 B 1.82 1.00 NA
D5863 A 1.69 0.48 NA
D5863 B 0.60 1.92 NA
A
Results for nitrogen determination by D4629 needed a sample dilution and ASTM did not publish a TPI value.

in the cross check. Thus, the low TPIs in Table 13 would 18. Future Directions
indicate laboratories determining sulfur (D2622 and D4294),
18.1 A number of areas remain of interest for further
nitrogen (D5762), organic chlorine (D4929), and metals by
both test methods (D5708 and D5863) need improvement in elemental characterization of crude oils. Some areas that have
their performance. been suggested for future work in elemental analysis of crude

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oils are described below. For several of these items, interlabo- 18.5 Multiple Elements by XRF—A study has been proposed
ratory studies have already started (18.4 through 18.9). to determine a suite of sulfur, chlorine, nickel, vanadium, iron,
and calcium in crude oils and residual fuels using PBMS
18.2 Mercury Speciation—There is substantial evidence that protocol. The samples will include sweet, sour, fracking, and
mercury can occur in crude oil as volatile, dissolved, and residual crude oils.
particulate (suspended) species, all of which differ consider-
ably in their chemical structure and behavior (1, 3). It would be 18.6 Chlorine—An extension of Test Methods D4929 for
desirable to have specific test methods to differentiate these this analysis is being pursued using WD-XRF, ED-XRF, and
MWD-XRF as alternative measurement techniques. Using the
mercury species.
sample preparation technique given in Test Methods D4929,
18.3 Selenium Speciation—Selenium has become a priority the crude oil samples will be first distilled to separate organic
pollutant because of its high toxicity to aquatic wildlife. In chlorine, and then determine the analyte with different XRF
refineries, it partitions into wastewater streams and can be techniques.
discharged from treatment plants into the environment where it 18.7 Multi-element Analysis using HD-XRF technique has
rapidly bioaccumulates (1, 3). As with mercury, selenium can been proposed. A ruggedness study has shown promising data
be present as different species that behave differently and for a number of samples for typical elements sulfur, chlorine,
complicate identification and remediation. Selenate [Se(VI)], nickel, vanadium, iron, and calcium.
selenite [Se(IV)], selenide [Se(-II)], colloidal selenium [Se(0)], 18.8 Halide by Combustion Ion Chromatography—An al-
and selenocyanate [SeCN-] have all been observed in waste- ternative measurement technique will be used after distillation
waters. In this study, analyzing 16 different crude oils total of crude oil fractions by Test Methods D4929, and subse-
concentration of selenium was found to range from < 10 to 960 quently determine chloride, bromide, fluoride, and possibly
µg/kg (15). At present there are no ASTM test method(s) for sulfate by aqueous ion chromatography.
the determination of selenium or its species in crude oil.
18.9 Microwave Plasma for Atomic Emission
18.4 Other Trace Elements—A number of trace elements are Spectroscopy—As an alternative to argon generated plasma,
now customarily included in the crude oil assay. Among these this technique uses nitrogen from air to generate the plasma.
are calcium, copper, iron, mercury, nickel, selenium, sodium, Axial magnetic and radial electrical fields sustain the nitrogen
and vanadium. The suite of elements will be dictated by plasma into which an aerosol of a sample diluted in 0-xylene is

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refinery processes, product slate, regulations and environmen- introduced. Promising preliminary results have been obtained
tal considerations (1). Analysis of some of these elements is for the determination of iron, nickel, vanadium, calcium,
mentioned above in this guide. Some alternative test methods sodium, and potassium in crude oils.
desirable for a suite of elements could be extending ICP-AES 18.10 Trace Elements using ICP-MS—Several oil industry
Test Method D5185, which can determine a large number of laboratories have been using this technique for many years for
trace elements but has not been applied to crude oils. X-ray the determination of very low levels of trace elements in crude
fluorescence spectrometry is not usually used for analyzing oils. A review of this area based on about 30 research papers
metals in crude oils given that the matrix effects could be a has been published by Hwang (16). This work is being
problem due to the presence of water and sediment in the undertaken in the Subcommittee D02.03 on Elemental Analy-
samples. sis of Petroleum Products and Lubricants.

REERENCES

(1) Giles, H. N., “Crude Oils,” Significance of Tests for Petroleum (6) Nadkarni, R. A., “Elemental Analysis of Crude Oils,” Elemental
Products, 8th ed., ASTM International, West Conshohocken, PA, Analysis of Fossil Fuels and Related Materials, ed. R. A. Nadkarni,
Chapter 8, 2010, pp. 106–122. ASTM International, West Conshohocken, PA, Monograph 10, Chap-
(2) Nadkarni, R. A., “Elemental Analysis of Crude Oils Using Spectro- ter 7, 2014, pp. 457–508.
scopic Methods,” Spectroscopic Analysis of Petroleum Products and (7) Nadkarni, R. A., “Sulfur: Chemistry and Analysis of Fossil Fuel
Lubricants, ed. R. A. Nadkarni, ASTM International, West Products,” ASTM International, West Conshohocken, PA, Monograph
Conshohocken, PA, Monograph 9, Chapter 23, 2011, pp. 605–624. 11, 2014.
(3) Giles, H. N., and Mills, C. O., “Crude Oils: Their Sampling, Analysis, (8) Nadkarni, R. A., “Guide to ASTM Test Methods for the Analysis of
and Evaluation,” ASTM International, West Conshohocken, PA, Petroleum Products and Lubricants,” ASTM International, West
Manual 68, 2010. Conshohocken, PA, Manual 44, 2nd edition, 2007.
(4) Nadkarni, R. A., A Review of Modern Instrumental Methods of (9) Long, S. E., Kelly, W. R., Mann, J. L., and Giles, H. N., “Determi-
Elemental Analysis of Petroleum Related Material: Part nation of Mercury in Crude Oils Using a Novel Method,” Proceed.
1—Occurrence and Significance of Trace Metals in Petroleum and 10th International Conf. on Stability, Handling, and Use of Liquid
Lubricants,” ed. Nadkarni, R. A., ASTM International, Philadelphia, Fuels, Tucson, AZ, Oct. 7-11, 2007.
PA, STP 1109, 1991, pp. 5–18. (10) Fox, B. S., Mason, K. J., and McElroy, F. C., “Determination of Total
(5) Filby, R. H. and Branthaver, J. F., “Metal Complexes in Fossil Fuels,” Mercury in Crude Oil by Combustion Cold Vapor Atomic Absorp-
American Chemical Society Symposium Series, No. 344, tion Spectrometry,” J. ASTM International, Vol. 2, No. 6, 2005, pp.
Washington, D.C., 1987. 13089.

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(11) Wilhelm, S. M., Kirchgessner, D. A., Liang, L., and Kariher, P. H., Data for Spectroscopic Analysis of Petroleum Products and
“Sampling and Analysis of Mercury in Crude Oil,” J. ASTM Lubricants,” Spectroscopic Analysis of Petroleum Products and
International, Vol. 2, No. 9, 2005, pp. 12985. Lubricants, ed. R. A. Nadkarni, ASTM International, West
(12) Nadkarni, R. A., Hwang, J. D., and Young, L., “Multielement Conshohocken, PA, Monograph 9, Chapter 4, 2011, pp. 74–111.
Analysis of Crude Oils Using Inductively Coupled Plasma Atomic (15) De Almeida, C. M. S., Ribeiro, A. S., Saint’Pierre, T. D., and
Emission Spectrometry,” J. ASTM International, Vol. 8, No. 10, Miekeley, N., “Studies on the Origin and Transformation of Sele-
2011, pp. 103837. nium and Its Chemical Species along the Process of Petroleum
(13) Nadkarni, R. A., “Proficiency Testing Programs for Elemental Refining,” Spectrochim. Acta B, Vol. 64, 2009, pp. 491–499.
Analysis of Fuels and Lubricants,” Elemental Analysis of Fossil (16) Hwang, J. D., “Applications of ICP-MS in the Petroleum Industry,”
Fuels and Related Materials, ed. R. A. Nadkarni, ASTM
Spectroscopic Analysis of Petroleum Products and Lubricants, ed. R.
International, West Conshohocken, PA, Monograph 10, Chapter 15,
A. Nadkarni, ASTM International, West Conshohocken, PA, Mono-
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graph 9, Chapter 9, 2011, pp. 208–2245.
(14) Bover, W. J., “Analyzing and Interpreting Proficiency Test Program

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