TRACE LEAD IN GASOLINES AND

NAPHTHAS BY GF-AAS

UOP 952-97

SCOPE

This method is for determining trace concentrations (10 to 400 mass/vol-ppb) of lead in gasolines and
petroleum naphthas. The method has not been validated on higher boiling range materials. The method is
specifically applicable to alkyl lead compounds such as tetraethyllead (TEL) and tetramethyllead (TML),
other lead compounds have not been investigated.

OUTLINE OF METHOD

Tetraalkyllead compounds in gasoline and naphthas are converted into water-soluble lead species that are
subsequently extracted into dilute nitric acid. Lead concentrations in the nitric acid extracts are determined
using Graphite Furnace-Atomic Absorption Spectrometry (GF-AAS).

APPARATUS

References to catalog numbers and suppliers are included as a convenience to the method user. Other
suppliers may be used.
Atomic absorption spectrometer, with autosampler and graphite furnace capabilities, Perkin-Elmer,
Model 4100ZL
Balance, top loading, readability 0.01-g
Cylinders, graduated, 25- and 100-mL, Fisher Scientific, Cat. Nos. 08-552C and -552E, respectively
Flasks, volumetric, Class A, borosilicate glass, 50-, 100-, 200- and 1000-mL, Fisher Scientific, Cat. Nos.
10-210-5B, -5C, -5D and -5G, respectively
Lamp, lead, EDL, Perkin-Elmer, Cat. No. N305-0657
Pipets, volumetric transfer, Class A, 1-, 3-, 5-, 10- and 50-mL, Fisher Scientific, Cat. Nos. 13-651-1A, -
1C, -1E, -1K and P, respectively

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 1997 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
service@astm.org, 610.832.9555 FAX, or 610.832.9585 PHONE.

Copyright by ASTM Int'l (all rights reserved);

Reproduction authorized per License Agreement with UOP; Thu Apr 29 07:23:50 EDT 2004
 2 of 5

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 distilled or deionized water.

References to catalog numbers and suppliers are included as a convenience to the method user. Other
suppliers may be used.

Ammonium dihydrogen phosphate, Puratronic, 99.998%, Alfa, Cat. No. 10633

Ammonium dihydrogen phosphate, 10% solution. Weigh 10.0 ± 0.01 g of ammonium dihydrogen
phosphate into a 100-mL volumetric flask, add 1 mL of concentrated nitric acid and dilute to volume
with water. Cap and shake well until dissolution is complete.

Bottle, Nalgene, 125-mL, Fisher Scientific, Cat. No. 03-313-2C

Cups, autosampler, polystyrene, Perkin-Elmer, Cat. No. B011-9079

Eye dropper, Nalgene, Fisher Scientific, Cat. No. 13-711-10

Iodine, Puratronic, 99.999%, Alfa, Cat. No. 10619

Iodine solution, 3%. Add 3.0 ± 0.01 g of iodine to a 100-mL volumetric flask and dilute with toluene to
the mark. Cap and shake until dissolved.

Lead standard solution, 1,000-µg/mL, SPEX CertiPrep, Cat. No. PLPB2-2Y

Lead standard solution, 10-µg/mL. Pipet 10 mL of the 1,000-µg/mL lead standard into a 1000-mL
volumetric flask, dilute to the mark with 10% nitric acid, cap and shake well. Lifetime of this standard
is one month.

Lead standard solution, 1-µg/mL. Pipet 10 mL of the 10-µg/mL lead standard into a 100-mL volumetric
flask, dilute to the mark with 10% nitric acid, cap and shake well. Lifetime of this standard is one
week.

Magnesium standard solution, 10,000-mg/L (1% Mg in 2% HNO3), SPEX Certiprep, Cat. No. PLMG2-
3Y

Nitric acid, concentrated, Ultrex II ultrapure reagent, J.T. Baker, Cat. No. 6901-05

Nitric acid, 10%. Mix one part concentrated nitric acid with nine parts water.

Toluene, Optima grade, Fisher Scientific, Cat. No. T291-4

PROCEDURE

The GF-AAS instrument is calibrated using an acid blank, and 15- and 30-µg/L lead standards. Samples
are then analyzed and the 30-µg/L standard is reanalyzed as a sample at the end of the run. A matrix
modifier composed of ammonium dihydrogen phosphate and magnesium nitrate is used to increase the
vaporization temperature of the lead.

952-97

Copyright by ASTM Int'l (all rights reserved);

Reproduction authorized per License Agreement with UOP; Thu Apr 29 07:23:50 EDT 2004
 3 of 5

The method as written yields a close approximation of the lead concentration in the sample, and is
considered adequate for its intended use. In the procedure below, some accuracy has been compromised for
speed. To generate data on a more accurate mass/mass basis, the standards would need to be prepared on a
mass/mass basis and the sample and nitric acid extract aliquots would also need to be weighed.

1. Pipet 10 mL of sample into a 120-mL Nalgene bottle, add 1 mL of 3% iodine solution and cap. Mix
the contents by shaking for 30 seconds. Set aside and allow the reaction to proceed for 10 minutes.
• If the sample is known to contain more than 150 mass/vol-ppb of lead, use a smaller sample size, or dilute
the resulting nitric acid extract. Although excess iodine is added to ensure complete reaction, this method
is not recommended for lead levels above 400 mass/vol-ppb. Use 1 mL of iodine solution regardless of the
sample size used.

2. Pipet 50 mL of 10% nitric acid solution into the bottle, cap and shake continuously for another 10
minutes. Allow a few minutes for the two layers to separate.

3. Take an aliquot of the lower aqueous layer using a Nalgene eye dropper and transfer to an
autosampler cup on the GF-AAS instrument.

4. Prepare fresh 15- and 30-µg/L calibration standards daily by pipeting separate 3 mL aliquots of the 1-
µg/mL lead standard solution into 200- and 100-mL volumetric flasks. Dilute to the mark with 10%
nitric acid, cap and shake well.

5. Prepare the matrix modifier solution by pipeting 10 mL of 10% ammonium dihydrogen phosphate
solution and 1 mL of 10,000-mg/L Mg standard solution into a 100-mL volumetric flask. Add 1 mL
of concentrated nitric acid, bring to the mark with water, cap and shake well.

6. Transfer aliquots of the matrix modifier, two calibration standards and an acid blank (10% nitric acid)
to separate autosampler cups on the GF-AAS instrument.

7. Set up the GF-AAS instrument according to the manufacturer’s instructions, using the conditions in
the Table.
• If an instrument other than the Perkin-Elmer Model 4100ZL is used, contact the instrument manufacturer
for help in determining appropriate settings for the instrument and furnace.

8. Enter the locations of the matrix modifier, acid blank, standards and sample(s) into the instrument
computer. Program the autosampler to take 5 µL of the matrix modifier and 20 µL of either the acid
blank, calibration standards or sample(s) with each injection.

9. Run the calibration (acid blank and two calibration standards), followed by the samples; and then run
the 30-µg/L standard as a sample to verify the calibration.
• The instrument autosampler will pick up 5 µL of the matrix modifier and 20 µL of acid blank, calibration
standard or sample, and inject both solutions together into the furnace. This provides 5 µg of phosphate
and 3 µg of magnesium nitrate to increase the vaporization temperature of the lead species.

• If the 30-µg/L calibration standard, when run as a sample, returns less than 28 µg/L lead or more than 32
µg/L lead, rerun the calibration and samples until a value between 28 and 32 µg/L lead is obtained.

• If the sample reading exceeds the calibration range of the standards, the acid extract may be diluted once
with 10% nitric acid.

952-97

Copyright by ASTM Int'l (all rights reserved);

Reproduction authorized per License Agreement with UOP; Thu Apr 29 07:23:50 EDT 2004
 4 of 5

Table
Instrument Parameters for the
Perkin-Elmer Model 4100 ZL

Wavelength 283.3 nm

Slit 0.7 nm

Background correction on

Sample size 20 µL

Dry temperature Step 1 140ºC 30 sec gas flow 250 mL/min

2 150ºC 20 sec “
3 200ºC 10 sec “
Ash temperature 4 850ºC 20 sec “
Atomize and read 5 1500ºC 5 sec “
Clean-out 6 2400ºC 2 sec “

Matrix modifier 5 µL of 10% NH4H2PO4 and 0.06% Mg(NO3)2

CALCULATIONS

Calculate the lead concentration using the equation and report results to two significant figures.

Lead, mass/vol-ppb = 5C
where:
C = concentration of lead in the solution read by GF-AAS, µg/L
5 = 50/10

where:
10 = volume of sample taken, mL
50 = volume of 10% HNO3 extract, mL

If a dilution of the extract was required to bring the sample reading within range of the standards,
multiply the dilution factor times the result from the equation to obtain the final result. If less than 10 mL of
sample was used (or available), substitute the actual volume used in place of 10 in the equation.

PRECISION
Repeatability

Based on eight tests performed by one analyst on one day in one laboratory, the within-laboratory
estimated standard deviations (esd) were calculated for lead in gasoline at the 133 and 28 µg/L levels. The
estimated standard deviations were 3.3 and 2.2 µg/L, respectively. Two tests performed in one laboratory by
the same analyst on different days should not differ by more than 11 or 7 µg/L, at the 133 and 28 µg/L
levels, respectively (the allowable differences at the 95% probability level).

952-97

Copyright by ASTM Int'l (all rights reserved);

Reproduction authorized per License Agreement with UOP; Thu Apr 29 07:23:50 EDT 2004
 5 of 5

The data quoted above is a “best case” estimate of the repeatability, and is equivalent to ASTM
repeatability statements. When the test is run routinely in the field, a control standard and chart should be
used to develop a better estimate of the long term repeatability.

Reproducibility

There is insufficient data to calculate the reproducibility of the test at this time.

TIME FOR ANALYSIS

The setup time may vary but once prepared a single sample can be run in 1.5 hours (elapsed time). The
labor requirement is 1.2 hours. Multiple samples run together will decrease the average elapsed time and
labor time requirements on a per sample basis.

REFERENCE

“Determination of Lead and Lead Isotope Ratios in Gasoline by Inductively Coupled Plasma-Mass Spec-
trometry”, Phillips Petroleum Company, Journal of Analytical Atomic Spectroscopy, May 1994, Vol. 9

SUGGESTED SUPPLIERS

Alfa, Johnson Matthey, P.O. Box 8247, Ward Hill, MA 01835-0747 (508-521-6300)
J.T. Baker Inc., 222 Red School Lane, Phillipsburg, NJ 08865 (908-859-2151)
Fisher Scientific, 711 Forbes Ave., Pittsburgh, PA 15219-4785 (412-562-8300)
Perkin-Elmer Corp., 761 Main Ave., Norwalk, CT 06859-0012 (203-762-1000)
SPEX CertiPrep, Inc., 203 Norcross Ave., Metuchen, NJ 08840-1253 (908-549-7144)

952-97

Copyright by ASTM Int'l (all rights reserved);

Reproduction authorized per License Agreement with UOP; Thu Apr 29 07:23:50 EDT 2004