TRACE METALS IN OILS BY

WET ASH / ICP—AES

UOP Method 389-86

SCOPE

This method is for determining iron, nickel, vanadium, lead, copper, sodium, molybdenum, manganese,
chromium, magnesium, tin, calcium, aluminum and zinc in crude petroleum, gas oils, fuel oils and jet fuels.
Most of the elements can be determined within the concentration range of 0.02 to 200 mass-ppm when a 50-
g sample of oil is ashed. Higher or lower concentrations can be determined by ashing appropriate-sized
samples. The method is sufficiently flexible to add more elemental determinations if needed.

OUTLINE OF METHOD

The oil sample is coked with fuming sulfuric acid, ignited and ashed at 538 C. The residue is then treated
with aqua regia and after evaporation is dissolved in dilute hydrochloric acid containing scandium and
lithium as internal standard and spectroscopic buffer, respectively. The resulting sample solutions are then
aspirated into a computer controlled, Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-
AES) along with appropriate standards. Concentrations are determined by comparison of the sample
emission signals to the computer-generated standard calibration curves.

APPARATUS
Balance, readability 0.01-g
Beaker, quartz, low form, 250-mL, Ace Glass Inc., Cat. No. 5334-14, or equivalent
Bottles, polypropylene, narrow mouth, screw cap, 1000-mL, Sargent-Welch Scientific, Cat. No. S-8420-
40F, or equivalent
Flask, volumetric, 10-, 50-and 1000-mL
Hot plate, variable heat, maximum operating temperature 510C
Muffle furnace, capable of operation at 538 C
Pipets, volumetric, transfer, Class A, 50-, 25-, 10-, 5-, 2- and 1-mL
Regulator, argon, two-stage, high purity, Matheson, Model 3104-580, or equivalent

IT IS THE USER’S RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO

DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND
SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS
PROCEDURE IN THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS
(MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN
THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION
EQUIPMENT (PPE).

© COPYRIGHT 1971, 1981, 1986 UOP LLC

ALL RIGHTS RESERVED

UOP Methods are available through ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken PA 19428-2959,
United States. The Methods may be obtained through the ASTM website, www.astm.org, or by contacting Customer Service at
[email protected], 610.832.9555 FAX, or 610.832.9585 PHONE.
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Regulator, nitrogen, two-stage, high-purity, Matheson, Model 3104-580, or equivalent

Spectrometer, Inductively Coupled Plasma-Atomic Emission Spectrometer, computer controlled, having

sufficient resolving power and dispersion to separate the analytical lines in the 160 to 800 nm region.
The computer should be capable of performing background corrections, blank corrections,
mass/volume corrections and dilution corrections. A commercial grating spectrometer with a band pass
of 0.018 nm or less in the first order is satisfactory.

Stirring rods, quartz, 16-cm. Prepare from quartz rod, 7-mm OD, Heraeus Amersil, TO8 commercial, or
equivalent.

REAGENTS AND MATERIALS

All reagents shall conform to the specifications established by the Committee on Analytical Reagents of
the American Chemical Society, when such specifications exist, unless otherwise specified. References to
water mean ASTM D 1193 Type I reagent grade water.

Aqua regia. Mix one volume of concentrated nitric acid with three volumes of concentrated hydrochloric
acid.

Argon, 99.995% minimum purity

Cleaning compound, detergent, Alconox, Sargent-Welch Scientific, Cat. No. S-19650, or equivalent

Hydrochloric acid, concentrated

Lithium solution, aqueous, 10,000 mass-ppm, SPEX Industries, Inc., Cat. No. PLLI-3X, or equivalent

Nitric acid, concentrated

Nitrogen, 99.99%, minimum purity

Scandium solution, aqueous, 1000 mass-ppm, SPEX Industries, Inc., Cat. No. PLSC-2, or equivalent

Scandium/lithium diluent. To prepare one liter, mix 50 mL of 1000 mass-ppm scandium solution, 100 mL
of 10,000 mass-ppm lithium solution and 100 mL of concentrated hydrochloric acid with 750 mL of
water. Store in a 1000-mL polypropylene bottle.

Standard metal solutions, Al, Fe, Ni, V, Sn, Mo, Cu, Pb, Na, Ca, Cr, Mg, Mn and Zn solutions of 1000
mass-ppm concentrations. SPEX Industries, Inc., Cat. Nos. PLAL-2, PLFE-2, PLNI-2, PLV-2, PLSN-
2, PLMO-2, PLCU-2, PLPB-2, PLNA-2, PLCA-2, PLCR-2, PLMG-2, PLMN-2 and PLZN-2,
respectively, or equivalent

Sulfuric acid, fuming, 27 to 30% excess SO3, Sargent-Welch Scientific, Cat. No. SC-17604, or equivalent

PREPARATION AND STANDARDIZATION OF APPARATUS

Preparation of Standards

A standard is required for each metal to be determined. Each standard should be prepared at
approximately the level expected in the sample or if the expected level is unknown, it is advisable to prepare
several standards to cover a wider concentration range (see Table 1). For convenience, a single standard can

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contain several metals. Prepare standards by appropriate dilution of standard metal solutions. Include a
blank. Pipet 50 mL of one of the prepared standard solutions into a 250-mL quartz beaker and evaporate to
dryness. Add 8 mL of fuming sulfuric acid and heat until all sulfur dioxide fumes have evolved. Place the
beaker in the muffle furnance at 538 C for one hour. Treat the mineral residue with about 2 mL of aqua
regia and evaporate to dryness. Dissolve the residue in 50 mL of scandium/lithium diluent. Follow this
procedure for all standards and the blank. Redetermine the blank each time a new bottle of fuming sulfuric
acid is opened.
Table 1
Elements Sought

Concentration Range
Element λ, nm in Sample, mass-ppm*
Fe 238.204 0.02-200
Ni 231.604 0.10-100
V 292.402 0.02-200
Cu 324.754 0.02-200
Pb 220.353 0.10-100
Na 589.592 0.05-500
Mo 202.030 0.05-50
Ca 393.366 0.05-5
422.673 5.0-500
Cr 206.149 0.05-50
Mg 279.553 0.02-200
Mn 257.610 0.02-200
Sn 189.989 0.20-200
Al 396.152 0.05-500
Zn 206.200 0.02-200
_____________
*Based on an ashed 50-g sample, diluted to 50 mL for the higher concentrations and 10 mL for the lower
concentrations.

Preparation of Spectrometer
Start up the ICP-AES and ignite the plasma according to the manufacturer’s recommendations. Allow a
minimum of 30 minutes warm up after the plasma is ignited before starting the analysis. Perform a
wavelength calibration prior to the start of the analysis if recommended by the manufacturer. Aspirate the
standards and blank to establish the calibration curves prior to aspiration of the samples. Table 1 lists
recommended wavelengths to be used for the analyses.

PROCEDURE

Sampling

Place samples in 250-mL quartz beakers that have previously been cleaned as follows: Wash the beakers
with cleaning compound and rinse with tap water. Add 10 mL of concentrated hydrochloric acid, bring to
boiling on a hot plate and rinse again 4 to 5 times with Type 1 water. Store in a clean area.

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Sample size depends primarily on the type of sample and the concentrations of metals expected to be
present. Several sample types and required amounts are listed in Table 2.

Table 2

Sample Amount, g
Asphalt 5 to 10
Vacuum Tower Bottoms
Vacuum Gas Oil 20 to 50
Fuel Oil
Jet Fuel 50 to 100
Atmospheric Gas Oil

Improper sampling can introduce significant errors into this method. Therefore, use care to ensure that a
representative sample of the total oil is obtained. Heat viscous samples gently until they flow freely; hot tap
water is generally satisfactory. However, more viscous samples may require use of a hot plate. Shake the
warmed samples vigorously or stir with a quartz rod and then weigh a sample for analysis to the nearest
0.01 g.

Wet Ashing

Add fuming sulfuric acid dropwise to the sample until vigorous reaction with light ends or traces of
moisture ceases. Add 8 mL of the acid for each 50 g of oil. After foaming has subsided, place the sample on
a hot plate and slowly apply heat. A slow increase in heating rate is necessary to avoid loss of sample by
“spitting” and will generally require about 12 hours before the maximum temperature is reached. Do not
exceed 538 C. Use the quartz stirring rod to break up any large pieces of char. After fuming has ceased and
the oil is completely charred, place the beaker with the char and stirring rod in a muffle furnance at 538 C
until all carbon is burned off (4 to 8 hours). Remove the beaker from the furnance and allow it to cool.
Dissolve the residue in 2 mL of aqua regia, being careful to wash down the stirring rod with aqua regia.
Evaporate to dryness and redissolve in 10-50 mL of scandium/lithium diluent, depending on the suspected
metal content of the sample.

Spectrometric Procedure

Prepare the spectrometer as described under Preparation of Spectrometer. Following aspiration of the
standards and blank, aspirate the samples after entering the appropriate mass per volume (and any
subsequent dilutions if necessary) in the computer. The computer will calculate the mass-ppm metal in the
original oil, and print the result.

CALCULATIONS

Calculate the mass-ppm of each element in the original oil using the raw mass-ppm value for each
element in the following equation.
R
C=
DW

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where:
C = concentration of a specific element in original oil, mass-ppm
D = dilution factor, volume pipeted divided by the final volume, if required
R = concentration of element in diluted sample, from instrument readout, mass-ppm
W = mass of oil used/original diluted volume

This calculation will normally be performed by the computer software after the analyst enters the
appropriate values for D and W.

PRECISION

The estimated standard deviations (esd) for various concentration levels of the metals determined by this
method are shown in the following table. Duplicate results by the same operator should not differ by more
than the amounts shown in the “allowable difference” column (95% probability).

Allowable
Level, esd, Difference, mass-
Metal mass-ppm mass-ppm ppm
Vanadium 380.0 4.0 13.0
Nickel 83.0 2.0 6.0
Sodium 42.0 0.4 1.5
Aluminum 4.1 0.6 2.3
Iron 0.9 0.1 0.5
Copper 0.40 0.01 0.03
Chromium 0.05 0.01 0.02
It is expected that all metals will have similar precision above one mass-ppm. Precision for levels below
one-ppm can vary depending on the limit of detection for the specific element.

TIME FOR ANALYSIS

The elapsed time for one analysis is 28 hours. The labor requirement for one analysis is 2 hours or in
groups of 5 or more samples, 1.5 hours.

REFERENCE

ASTM Method D 1193, www.astm.org

SUGGESTED SUPPLIERS

Ace Glass Inc., P.O. Box 688, Vineland, NJ 08360

Heraeus Amersil, 650 Jernees Mill Rd., Sayreville, NJ 08872
Matheson, P.O. Box 96, Joliet, IL 60434
Sargent-Welch Scientific Co., 7300 N. Linder Ave., Skokie, IL 60077
SPEX Industries, Inc., P.O. Box 798, Metuchen, NJ 08840

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