Designation: D7111 − 16

Standard Test Method for

Determination of Trace Elements in Middle Distillate Fuels
by Inductively Coupled Plasma Atomic Emission
Spectrometry (ICP-AES)1
This standard is issued under the fixed designation D7111; 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* D3605 Test Method for Trace Metals in Gas Turbine Fuels
1.1 This test method covers the determination of selected by Atomic Absorption and Flame Emission Spectroscopy
elements in middle distillate fuels by inductively coupled D4057 Practice for Manual Sampling of Petroleum and
plasma atomic emission spectrometry (ICP-AES). The specific Petroleum Products
elements are listed in Table 1. The concentration range of this D4306 Practice for Aviation Fuel Sample Containers for
test method is approximately 0.1 mg ⁄kg to 2.0 mg/kg. The test Tests Affected by Trace Contamination
method may be used for concentrations outside of this range; D5185 Test Method for Multielement Determination of
however, the precision statements may not be applicable. Used and Unused Lubricating Oils and Base Oils by
Middle distillate fuels covered in this test method have all Inductively Coupled Plasma Atomic Emission Spectrom-
distillation fractions contained within the boiling range of etry (ICP-AES)
150 °C to 390 °C. This includes, but is not limited to, diesel D6299 Practice for Applying Statistical Quality Assurance
fuels and aviation turbine fuels. and Control Charting Techniques to Evaluate Analytical
Measurement System Performance
1.2 This test method is not intended to analyze insoluble D6792 Practice for Quality System in Petroleum Products
particulates. However, very small particulate matter (smaller and Lubricants Testing Laboratories
than a micrometre) will be carried into the plasma and be D7260 Practice for Optimization, Calibration, and Valida-
included in the quantitative analysis. tion of Inductively Coupled Plasma-Atomic Emission
1.3 This test method may give a result that is higher than the Spectrometry (ICP-AES) for Elemental Analysis of Petro-
true value if an analyte is present in the sample in a form which leum Products and Lubricants
is sufficiently volatile. For example, hexamethyldisiloxane will 2.2 Military Standard:
generate a biased high result for silicon. MIL-DTL-16884 Fuel, Naval Distillate3
1.4 The values stated in SI units are to be regarded as
standard. 3. Terminology
1.5 This standard does not purport to address all of the 3.1 Definitions:
safety concerns, if any, associated with its use. It is the 3.1.1 calibration, n—the determination of the values of the
responsibility of the user of this standard to establish appro- significant parameters by comparison with values indicated by
priate safety and health practices and determine the applica- a set of reference standards.
bility of regulatory limitations prior to use. 3.1.2 calibration curve, n—the graphical or mathematical
2. Referenced Documents representation of a relationship between the assigned (known)
values of standards and the measured responses from the
2.1 ASTM Standards:2 measurement system.
D2880 Specification for Gas Turbine Fuel Oils
3.1.3 calibration standard, n—a standard having an ac-
1
This test method is under the jurisdiction of ASTM Committee D02 on
cepted value (reference value) for use in calibrating a measure-
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of ment instrument or system.
Subcommittee D02.03 on Elemental Analysis. 3.1.4 detection limit, n—a stated limiting value that desig-
Current edition approved Dec. 1, 2016. Published December 2016. Originally
approved in 2005. Last previous edition approved in 2015 as D7111 – 15a. DOI: nates the lowest concentration that can be determined with
10.1520/D7111-16. confidence and that is specific to the analytical procedure used.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
3
the ASTM website. Available online at http://quicksearch.dla.mil or http://assistdocs.com

*A Summary of Changes section appears at the end of this standard

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

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 D7111 − 16
TABLE 1 Elements and Recommended Wavelengths TABLE 2 Internal Standards, Recommended Wavelengths, and
Element Wavelengths, nm Approximate Use Concentrations
Aluminum 308.215, 396.153 Internal Wavelength, Concentration,
Barium 455.403, 493.408 Standard nm mg/kg
Calcium 393.366 Scandium 361.383 1-2
Chromium 267.716, 283.563 Yttrium 371.029 1-5
Cobalt 228.615, 236.375, 238.892
Copper 324.752
Iron 259.939
Lithium 670.784
Lead 220.353, 224.688, 283.306
Magnesium 279.553
5. Significance and Use
Manganese 257.610 5.1 Trace elemental analysis is used to indicate the level of
Molybdenum 202.030, 204.597, 281.616
Nickel 221.648, 341.476 contamination of middle distillate fuels. Trace metals in turbine
Phosphorus 177.495, 178.287, fuels can cause corrosion and deposition on turbine compo-
185.944, 214.914, 213.618 nents at elevated temperatures. Some diesel fuels have speci-
Palladium 340.458, 342.124
Platinum 214.423 fication limit requirements for trace metals to guard against
Potassium 766.490 engine deposits. Trace level copper in middle distillate aviation
Sodium 588.995 turbine fuel can significantly accelerate thermal instability of
Silicon 251.611
Silver 328.068 the fuel, leading to oxidation and production of detrimental
Strontium 407.771 insoluble deposits in the engine.
Tin 283.999, 189.991
Titanium 334.940 5.2 Gas turbine fuel oil Specification D2880 provides rec-
Vanadium 310.230 ommended upper limits for five trace metals (calcium, lead,
Zinc 213.857
sodium, potassium, and vanadium). Military specification
MIL-DTL-16884 for naval distillate fuel sets requirements for
maximum concentrations of the same five metals. Both speci-
fications designate Test Method D3605, an atomic absorption/
3.1.5 emission spectroscopy, n—measurement of the energy flame emission method, for the quantitative analysis of four of
spectrum emitted by or from an object under some form of the metals. Test Method D3605 does not cover potassium. This
energetic stimulation; for example, light or electrical discharge. test method provides an alternative to Test Method D3605,
3.1.6 inductively coupled plasma, n—a high temperature covers potassium and a number of additional elements.
discharge generated by passing an ionizable gas through a 5.3 There are several sources of multi-element contamina-
magnetic field induced by a radio frequency coil surrounding tion of naval distillate fuel. Sea water is pumped into the diesel
the tubes that carry the gas. fuel tanks (as ballast) to trim ships. Also, some of the oilers
3.1.7 radio frequency, n—the range of frequencies between (fuel supply ships) have dirty tanks. Corrosion products come
3 kHz and 300 GHz. from unlined tanks, piping, pumps, and heat exchangers.
3.1.8 standard, n—a physical or chemical reference used as
a basis for comparison or calibration. 6. Interferences

3.2 Definitions of Terms Specific to This Standard: 6.1 Elemental wavelengths listed in Tables 1 and 2 have
3.2.1 detection limit, n—the lowest concentration value for been found to be free of spectral interferences with all other
an element that can be determined by ICP analysis and that is elements listed in Tables 1 and 2 in the concentration range of
calculated by multiplying three times the standard deviation of this test method.
ten repetitive element analyses of the blank solution. 6.2 If a spectral interference does exist, then selecting an
3.2.2 internal standard, n—a chemical standard having an analytical wavelength other than those listed in Table 1 or
accepted value (and added to the fuel test specimen and Table 2 may be used as long as the new wavelength possesses
calibration standard) to determine the emission intensity ratio appropriate sensitivity for the scope of the method.
of an element to the internal standard. 6.3 Alternatively, the ICP spectrometer manufacturer’s soft-
ware may be used to provide corrections to interferences that
4. Summary of Test Method cannot be avoided by wavelength selection and background
4.1 Calibration standards are prepared by mixing organo- correction.
metallic standard materials in kerosine. An internal standard 6.4 An empirical method for correcting for spectral inter-
material is added to the calibration standards and fuel samples. ferences is detailed in Test Method D5185, Section 6.1
The calibration standards and the fuel samples are aspirated (Spectral).
into the ICP-AES instrument. The concentrations of the ele-
ments in the fuel are calculated by comparing emission 7. Apparatus
intensity ratios of the fuel and calibration standards to the 7.1 Inductively-Coupled Plasma Atomic Emission
internal standard. Spectrometer—Any commercial sequential or simultaneous
4.2 Consult Practice D7260 regrading the optimum opera- ICP-AES instrument capable of measuring emission intensities
tion of any ICP-AES system. of the elements of interest (and listed in Table 1). A vacuum or

2
 D7111 − 16
inert gas optical path is required for analysis of any element at 8.7 Nitric Acid, 10 % aqueous solution. (Warning—Nitric
wavelengths below 190 nm. acid may cause severe burns.)
7.2 Nebulizer—For samples without particulates, a concen- 8.8 Quality Control (QC) Samples, preferably are portions
tric nebulizer is recommended to provide higher sensitivity for of one or more fuel or kerosine materials that are stable and
low concentrations and for low sensitivity elements. For representative of the samples of interest. These QC samples
unknown samples, a Babington-type high solids nebulizer is can be used to check the validity of the testing process as
recommended to reduce the possibility of clogging from described in Section 18. If a suitable QC fuel is not available,
particulate. obtain a stable QC concentrate, and dilute it with kerosine on
7.3 Spray Chamber, suitable for organic materials. the day of the QC check to the trace level required as described
in 12.3. Use HDPE plastic bottles to contain concentrated
7.4 Peristaltic Pump—A peristaltic pump is required to organometallic solutions and for sodium analysis.
provide a constant flow of liquid to the ICP. Viton pump tubing
is recommended for use with fuels and kerosine. 9. Hazards
7.5 Membrane Filter, 47 mm diameter, 0.8 µm or 1.0 µm 9.1 Gases under high pressure and corrosive acid are used in
pore size. this method. Wear appropriate personal protective equipment
7.6 Membrane Filter Holder Assembly, for 47 mm diameter when working with nitric acid. Use only apparatus rated for
filters, with filtration flask. handling the high gas pressures that occur in this test method.
7.7 Pipette, 1000 µL. 10. Sampling and Test Specimens
7.8 Volumetric Flasks, 25 mL and 50 mL, glass. 10.1 Samples shall be taken in accordance with procedures
7.9 Glass or High Density Polyethylene (HDPE) Bottles, described in Practice D4057. Suitable sample containers for
125 mL, round. aviation fuels are described in Practice D4306. Use HDPE
plastic containers for sodium analysis.
7.10 Analytical Balance, measuring to 0.0001 g.
10.2 Samples shall be thoroughly mixed in their containers
8. Reagents and Materials immediately prior to testing.
8.1 Purity of Reagents—Reagent grade chemicals shall be 10.3 If particulate matter is observed in the sample, filter it
used in all tests. Unless otherwise indicated, it is intended that through a 0.8 µm or 1.0 µm (nylon, TFE-fluorocarbon, cellu-
all reagents conform to the specifications of the Committee on lose acetate/cellulose nitrate, or other compatible material)
Analytical Reagents of the American Chemical Society where membrane filter into an acid-cleaned flask and retain the filtrate
such specifications are available.4 Other grades may be used, for analysis. Follow the same filtration procedure for the
provided it is first ascertained that the reagent is of sufficiently kerosine blank material used for the analysis of these samples.
high purity to permit its use without lessening the accuracy of
11. Preparation of Apparatus
the determination.
11.1 Spectrometer—Prepare the ICP spectrometer according
8.2 Organometallic Standards, single element and multiele-
to the manufacturer’s instructions and parameter settings for
ment organometallic standards, nominal 100 mg/kg of each
organic materials and the elements of interest. At least three
element of interest.
integrations should be made for all samples (standards, blank,
8.3 Internal Standard, fuel soluble yttrium, cobalt, scan- fuels) run. Table 1 provides recommended element wave-
dium or other single element organometallic standard, not a lengths for fuels; however, other wavelengths may be used due
component of the fuel test specimen or calibration standard, to possible instrument variations or spectral interferences. The
nominal 5000 mg/kg. optical path can be purged with argon or another high purity
8.4 Kerosine, with analyte concentrations below the detec- gas (for example, nitrogen) recommended by the manufacturer.
tion limits of the instrument. The kerosine can be screened for Before igniting the plasma, inspect the quartz torch to make
the presence of analytes as detailed in 12.1 by performing a sure that it is clean. If carbon build-up is observed, replace the
wavelength scan for analyte wavelengths. torch and make the manufacturer’s recommended adjustments
for this problem. Warm up the instrument while purging the
8.5 Argon Gas, 99.995 % minimum purity. (Warning— optics for the time period recommended by the ICP manufac-
Argon may be a compressed gas under high pressure.) turer. If necessary, replace the peristaltic pump tubing and
8.6 Nitrogen Gas, 99.999 % minimum purity. (Warning— adjust the solution uptake to the desired rate. Ignite the torch,
Nitrogen may be a compressed gas under high pressure.) then begin aspirating kerosine through the nebulizer and into
the spray chamber. Continue plasma warm-up/stabilization for
the duration specified by the ICP manufacturer.
4
Reagent Chemicals, American Chemical Society Specifications, American 11.2 Glassware, Plasticware—Acid clean glassware and
Chemical Society, Washington, DC. For Suggestions on the testing of reagents not plasticware with 10 % nitric acid (trace metal analysis grade)
listed by the American Chemical Society, see Annual Standards for Laboratory
followed by several distilled water rinses. Do not use glassware
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, and plasticware that has previously contained solutions with
MD. high concentrations of the element(s) of interest.

3
 D7111 − 16
12. Preparation of Standards and Test Specimens est) into the container. Add kerosine to bring the solution mass
to a nominal 50.0 g. Determine the solution mass to the nearest
12.1 Purity of Kerosine—Sources of satisfactory high purity
0.0001 g. Seal the container and mix the solution well.
kerosine are commercially available. For ICP instruments
Calculate the element concentrations as shown in 16.1. Use
which provide a visual profile of emission peaks, a check may
these values for establishing the calibration lines (see Section
be made of the kerosine purity by aspirating the kerosine and
14). The calibration standard solution is to be prepared daily
viewing the spectral regions where the element emissions of
when samples are to be analyzed.
interest are to be found. The absence of emission peaks in these
12.3.3 Working Standard—The working standard is pre-
regions is evidence that the purity is satisfactory.
pared with the calibration standard solution and the internal
12.2 Internal Standard Stock Solution: standard stock solution as follows: To a 50 mL volumetric
12.2.1 The analyst’s selection of the single element internal flask, pipette 1000 µL of the internal standard stock solution.
standard may be influenced by the capabilities (wavelength Fill the volumetric flask to the volume mark with the calibra-
availability, sensitivity) of the ICP instrument available. The tion standard solution prepared in 12.3.2. Seal the volumetric
single element chosen for the internal standard should not be a flask and mix well. Working standards are to be prepared daily
component of the fuel test specimen or calibration standard. when samples are to be analyzed.
Organometallic yttrium has performed well as an internal 12.3.3.1 Use of the yttrium internal standard stock solution
standard for this test method and is recommended. Table 2 lists described in 12.2.3 will provide a nominal 1.0 mg/kg internal
internal standards, their recommended wavelengths, and their standard in the working standard.
approximate use concentrations for this test method. 12.4 Check Standard—Prepare an instrument check stan-
12.2.2 Prepare a stock solution of the internal standard by dard in the same manner as the working standard (see 12.3) at
weight from a 5000 mg/kg single element organometallic element concentrations that are anticipated for the fuel samples
standard material and kerosine. Prepare a concentration that is to be analyzed. It is advisable to prepare the check standard
approximately 50 times the concentration required in the fuel from an alternative source of certified organometallic standard.
test specimen and working standard. Prepare a minimum of 50
grams of internal standard stock solution. Prepare fresh internal 12.5 Test Specimens—To a 50 mL volumetric flask, add
standard stock solution weekly. 1000 µL of the internal standard stock solution. Fill the flask to
the mark with the fuel to be analyzed. This provides a fuel test
12.2.3 The following is an example for preparing a nominal
specimen with an internal standard at the same concentration as
50 mg/kg yttrium internal standard stock solution: Tare on an
provided in the working standard. If insufficient fuel sample is
analytical balance a clean glass or HDPE plastic container (for
available, the flask volume and added internal standard stock
example, 125 mL bottle, use HDPE for sodium analysis) sized
solution volume may be proportionally reduced. Since the
for the following procedure. Weigh a nominal 0.5 g (to the
same amount of internal standard stock solution has been
nearest 0.001 g) of the 5000 mg/kg yttrium organometallic
added to the working standard and the fuel test specimens, no
internal standard into the container. Add kerosine to bring the
dilution factor correction is needed.
solution mass to a nominal 50.0 g. Determine the solution mass
to the nearest 0.001 g. Seal the container and mix well. The 13. Wavelength Selection and Background Correction
internal standard stock solution concentration is determined in
the same manner as described for the calibration standard in 13.1 Recommended wavelengths for each element to be
16.1. determined and for internal standards are given in Table 1 and
Table 2, respectively. To accommodate different ICP instru-
12.3 Working Standard: ments and their performances, other wavelengths not shown in
12.3.1 Preparation of a nominal 2.0 mg/kg elemental work- these tables may be used. Select wavelengths with best
ing standard is described in this test method as an example. intensity, peak shape, and lack of interferences. Since analyses
Higher or lower working standard concentrations may be are for trace levels of elements, background correction is
prepared depending on the sensitivity of the ICP spectrometer required. Thus, for all elements possible, the baseline for the
(for example, radial or axial viewing, detector type, age of ICP) emission peak should be set with points as close to both sides
and the elements of interest in the fuel sample. Determine the of the peak without measuring the element wavelength inten-
suitability of the working standard concentration after calibra- sity (see Fig. 1). After these baselines are set, a check standard
tion by analyzing a kerosine sample prepared with a known is used to test the system response and calibration as described
concentration (for example, 1.0 mg/kg) of the elements of in the next section.
interest. Measured values within 5 % of the prepared concen- 13.2 Appropriate selection of wavelengths for background
tration are acceptable. Commercially available organometallic corrections is extremely critical for the determination of
standards with certified element concentrations are suitable for sodium since the predominate sodium emission line
this test method. (588.995 nm) resides near a significant argon emission inter-
12.3.2 Calibration Standard Solution (nominal ference. During method development it is recommended, if
2.0 mg ⁄kg)—Tare on an analytical balance a clean glass or possible, that the spectra of samples and standards be com-
HDPE plastic container (for example, 125 mL bottle, use pared at the sodium emission wavelength to ensure that signal
HDPE for sodium analysis) sized for the following procedure: integration occurs accurately.
Weigh a nominal 1.0 g (to the nearest 0.0001 g) of the nominal NOTE 1—Some emission wavelengths occur on a highly structured
100 mg ⁄kg organometallic standard (for all elements of inter- background (for example, sodium emission at 588.995 nm); hence a single

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 D7111 − 16

FIG. 1 Correct (A) and Incorrect (B) Selection of Background

off-peak background measurement may provide inaccurate results. For section and Section 15 pertain to baseline corrected peak areas.
emission wavelengths on a structured background, background correction The calibration curve is a plot of the intensity ratio for an
is recommended at both lower and higher wavelengths from the emission
wavelength. In addition, some low-resolution, photomultiplier tube-based
element e in the working standard (Rws) versus the concentra-
instruments may require a comprised selection of background points, tion of element e in the calibration standard (Ccs), and
which could also provide inaccurate results.
R ws 5 ~ I ws 2 I b ! /I ints (1)
14. Calibration where:
14.1 A two-point calibration, consisting of the kerosine Iws = emission intensity for element e in the working
blank and the working standard, of the instrument is conducted standard,
within the linear range of the spectrometer. Calibration shall be Ib = emission intensity for element e in the kerosine blank,
performed each time a new batch of fuel samples is to be and
analyzed. Iints = emission intensity of the internal standard in the
14.2 Analyze the check standard to determine if all elements working standard solution.
are in calibration. Each element must be within 5 % of its 15. Analysis
prepared concentration in order to proceed to testing of fuel 15.1 Determine the ICP detection limits for all elements of
samples. If not, make necessary instrument adjustments and interest as follows: Prepare a kerosine blank with an internal
recalibrate until all elements are within 5 % of check standard standard by pipetting 1000 µL of the internal standard stock
values. solution into a 50 mL volumetric flask, and fill to the volume
14.3 Aspirate kerosine between standard (and fuel test marker with kerosine. Seal the flask, and mix well. Perform ten
specimen) runs to purge the system of elements prior to the consecutive analyses of this solution for all elements of interest
next run. If high element concentrations have been run, check under the same conditions/parameters that the two-point cali-
the element signal intensity after the kerosine purge to ensure bration standards were run. With the ICP instrument software,
that it has been removed. determine the standard deviation of the ten results for each
14.4 Most ICP spectrometers have software that automati- element of interest. The detection limit of each element is its
cally performs the calculations to establish the calibration standard deviation multiplied by three. Detection limits should
curve when using an internal standard. Element emission be determined daily after calibration.
intensities are ratioed to the internal standard emission inten- 15.2 Conduct fuel sample analyses under the same
sities. Subsequent references to emission intensities in this conditions/parameters that the two-point calibration standards

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 D7111 − 16
were run. Aspirate kerosine between fuel samples to clear the M100 = the mass (g) of the nominal 100 mg/kg organome-
system of elements from the prior sample. The ICP instrument tallic standard, and
software generates concentration values for each element. Mcs = the mass (g) of the prepared solution of the nominal
15.3 In a manner similar to that described in 14.4 for the 100 mg/kg organometallic standard and kerosine.
calibration, the analysis of the fuel sample generates an 17. Report
intensity ratio as follows:
17.1 Report element concentrations in mg/kg to two deci-
R f 5 I f /I intf (2)
mal places. If a concentration is determined to be below the
where: detection limit (BDL) of the instrument, it should be identified
Rf = intensity ratio for an element e in the fuel, as such (BDL) along with the determined detection limit for the
If = emission intensity of element e in the fuel, and element.
Iintf = emission intensity of internal standard added to the
fuel. 18. Quality Control
18.1 Confirm the performance of the instrument or the test
Thus, by comparison with the calibration curve, the ICP
procedure by analyzing a quality control (QC) sample (see
instrument software determines the element concentrations as
8.8).
follows:
18.1.1 If a suitable QC fuel sample is not available, prepare
C f 5 ~ R f 3 C cs! /R ws (3) QC samples daily from the QC concentrate at different con-
where: centrations in the working range in the same manner described
in 12.3.
Cf = concentration (mg/kg) of element e in the fuel,
Ccs = concentration (mg/kg) of element e in the calibration 18.1.2 When QC/quality assurance (QA) protocols are al-
standard, ready established in the testing facility, these may be used
Rf = intensity ratio of element e in the fuel, and when they confirm the reliability of the test result.
Rws = intensity ratio of element e in the working standard. 18.1.3 When there is no QC/QA protocol established in the
testing facility, Appendix X2 can be used as the QC/QA
15.3.1 Eq 3 applies if the density of the working standards system.
and the test specimen are similar. If the density of the test
specimen is dissimilar (greater than 6 %) to that of the working 19. Precision and Bias
standards, the accuracy of the result calculated by Eq 3 will be 19.1 Precision—The precision of this test method was
impacted. The effect of the density difference can be corrected determined by the statistical examination of two interlabora-
for by multiplying the result of Eq 3 (Cf) by the density of the tory studies.5 The first interlaboratory study involved eight
working standard divided by the density of the test specimen. laboratories and twelve fuel samples analyzed in duplicate (six
Alternatively, the working standards can be prepared using a diesel, three aviation jet, and three kerosine fuels spiked with
diluent of similar density to that of the test specimen. organometallics at varied levels within the range of the
NOTE 2—The procedure described in 15.3 only works if the internal method). The second interlaboratory study (a rerun of sodium
standard fully compensates for sample transport and nebulization differ- only, using HDPE sample bottles) involved six laboratories and
ences between the sample and the standard. This may not be the case for twelve fuel samples analyzed in duplicate (six diesel, three
larger density differences. However, the middle distillate fuels covered in aviation jet, and three kerosine fuels spiked with organometal-
this test method have all distillation fractions contained within the boiling
range of 150 °C to 390 °C and the differences in density typically should
lics at varied levels within the range of the test method). The
not be significant enough to cause sample transport and nebulization precision determined is as follows:
differences. 19.1.1 Repeatability—The difference between successive
results obtained by the same operator with the same apparatus
15.4 Analyze the check standard after every fifth fuel test
under constant operating conditions on identical test material
specimen. If any result is not within 5 % of the prepared
would, in the long run, in the normal and correct operation of
concentration, recalibrate the instrument and reanalyze the
the test method, exceed the values in Table 3 only in one case
previously analyzed fuel test specimens back to the previously
in twenty.
acceptable check standard analysis.
19.1.2 Reproducibility—The difference between two single
and independent results obtained by different operators work-
16. Calculation
ing in different laboratories on identical test material would in
16.1 Calculate the concentrations of the elements in the the long run, exceed the values in Table 4 only in one case in
calibration standard solution as follows: twenty. Calculated reproducibility (and repeatability) values
for a 1.0 mg/kg result are shown in Table 5.
C cs 5 ~ M 100/M cs! C 100 (4)
19.2 Bias—Since there are no accepted reference materials
where: for determining bias for this test method, no statement on bias
Ccs = the concentration (mg/kg) of element e in the cali- is being made.
bration standard solution,
C100 = the concentration (mg/kg) of element e in the nomi- 5
Supporting data have been filed at ASTM International Headquarters and may
nal 100 mg/kg organometallic standard,
be obtained by requesting Research Report RR:D02-1569.

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 D7111 − 16
TABLE 3 Repeatability TABLE 4 Reproducibility
A B
Range, Repeatability, Range,A Reproducibility,B
Element Element
mg/kg mg/kg mg/kg mg/kg
Aluminum 0.13 – 1.77 0.09692 X0.5202 Aluminum 0.13 – 1.77 0.3689 X0.5202
Barium 0.11 – 1.92 0.05896 X0.7520 Barium 0.11 – 1.92 0.2353 X0.7520
Calcium 0.10 – 1.77 0.0887 X0.7391 Calcium 0.10 – 1.77 0.3097 X0.7391
Chromium 0.11 – 1.73 0.05839 X1.0350 Chromium 0.11 – 1.73 0.2869X1.0350
CobaltC 0.15 – 1.60 0.2007 (X + 0.0001)0.4577 CobaltC 0.15 – 1.60 0.8508 (X + 0.0001)0.4577
Copper 0.11 – 1.85 0.03470 (X + 0.6579) Copper 0.11 – 1.85 0.2495 (X − 0.09548)
Iron 0.11 – 1.71 0.05312 X0.9114 Iron 0.11 – 1.71 0.2717 X0.9114
Lithium 0.10 – 1.83 0.06941 (X − 0.02484) Lithium 0.10 – 1.83 0.09703 (X + 0.4716)
Lead 0.08 – 1.73 0.1166 X0.6934 Lead 0.08 – 1.73 0.6039 X0.6934
Magnesium 0.10 – 1.76 0.04820 X0.6570 Magnesium 0.10 – 1.76 0.2200 X0.6570
Manganese 0.10 – 1.75 0.04522 X0.9759 Manganese 0.10 – 1.75 0.2517 X0.9759
Molybdenum 0.11 – 1.74 0.08204 X0.9591 Molybdenum 0.11 – 1.74 0.3725 X0.9591
Nickel 0.10 – 1.72 0.05274 (X + 0.3444) Nickel 0.10 – 1.72 0.2811 (X – 0.01824)
PhosphorusC 0.20 – 1.80 0.1396 X0.522 PhosphorusC 0.20 – 1.80 1.3089 X0.522
Potassium 0.19 – 1.80 0.1191 X0.3661 Potassium 0.19 – 1.80 0.5212 X0.3661
PalladiumC 0.12 – 1.88 0.1530 X0.9144 PalladiumC 0.12 – 1.88 1.1924 X0.9144
PlatinumC 0.49 – 1.52 0.2288 X0.7489 PlatinumC 0.49 – 1.52 1.3488 X0.7489
Sodium 0.21 – 2.03 0.02916 (X + 1.8414) Sodium 0.21 – 2.03 0.2433 (X + 1.8414)
Silicon 0.17 – 1.95 0.07106 X0.3976 Silicon 0.17 – 1.95 0.2399 X0.3976
Silver 0.08 – 2.02 0.07236 X0.5626 Silver 0.08 – 2.02 0.3025 X0.5626
StrontiumC 0.08 – 1.78 0.1557 (X + 0.0125)0.6319 StrontiumC 0.08 – 1.78 0.7512 (X + 0.0125)0.6319
TinC 0.38 – 1.43 0.1099 (X + 0.0241)0.2606 TinC 0.38 – 1.43 0.9926 (X + 0.0241)0.5275
Titanium 0.11 – 1.73 0.04993 X0.6002 Titanium 0.11 – 1.73 0.2175 X0.6002
Vanadium 0.10 – 1.72 0.06637 X0.5841 Vanadium 0.10 – 1.72 0.3359 X0.5841
Zinc 0.09 – 1.65 0.05507 X0.7402 Zinc 0.09 – 1.65 0.3593 X0.7402
A A
Range of sample means in interlaboratory study. Range of sample means in interlaboratory study.
B B
Where X is the mean concentration, mg/kg. Where X is the mean concentration, mg/kg.
C C
Interim equations based on limited ILS. Supporting data have been filed at ASTM Interim equations based on limited ILS. Supporting data have been filed at ASTM
International Headquarters and may be obtained by requesting Research Report International Headquarters and may be obtained by requesting Research Report
RR:D02-1778. RR:D02-1778.

20. Keywords
20.1 aviation turbine fuel; diesel fuel; elemental analysis;
fuel; ICP; inductively coupled plasma atomic emission spec-
trometry; internal standard; middle distillate fuels; trace
elements

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 D7111 − 16
TABLE 5 Calculated Precision, mg/kg, at 1.0 mg/kg
Repeatability, Reproducibility,
Element
mg/kg mg/kg
Aluminum 0.097 0.369
Barium 0.059 0.235
Calcium 0.089 0.310
Chromium 0.058 0.287
Cobalt 0.201 0.851
Copper 0.035 0.226
Iron 0.053 0.272
Lithium 0.069 0.143
Lead 0.117 0.604
Magnesium 0.048 0.220
Manganese 0.045 0.252
Molybdenum 0.082 0.373
Nickel 0.071 0.276
Phosphorus 0.1369 1.309
Potassium 0.119 0.521
Palladium 0.153 1.192
Platinum 0.229 1.349
Sodium 0.083 0.691
Silicon 0.071 0.240
Silver 0.072 0.303
Strontium 0.157 0.757
Tin 0.111 1.005
Titanium 0.050 0.218
Vanadium 0.066 0.336
Zinc 0.055 0.359

APPENDIXES

(Nonmandatory Information)

X1. HELPFUL HINTS FOR OPERATION OF TEST METHOD D7111

X1.1 Follow good laboratory practice when handling X1.6 To minimize contamination during standard/sample
samples. Some samples may have very low levels of analytes. preparation, prepare all aliquots in either PP or FEP/PFA
All samples should be handled with extreme care to avoid pre-cleaned containers. The sample introduction system should
contamination. The sample containers should be opened only be cleaned and maintained periodically based on sample
when ready for analysis. volume and analyte concentration.

X1.2 Work in a well-ventilated hood, and with adequate X1.7 Select solvents and other reagents that do not contain
protection as prescribed in the appropriate safety practices. significant levels of the analytes being determined.

X1.3 Check the temperature and humidity controls of the X1.8 It is extremely important to homogenize samples in
laboratory containing the ICP-AES instrument, and verify the original sample container in order to obtain a representative
adequacy for performing accurate and precise analyses. Ensure test sample. Employ adequate mixing and sampling
that stable environmental conditions exist throughout the procedures, especially for heavier samples. If using hand
period of use. shaking, vigorously shake the sample container for about 30 s
immediately prior to taking an aliquot for analysis. Ultrasonic
X1.4 Contamination is a common occurrence in the analyti- homogenizers and vortex mixers can help in making the
cal laboratory and can be difficult to control unless proper samples uniform in their content.
precautions are taken. Ensure that all glassware and so forth
that contacts samples and standards does not contaminate the X1.9 If particulates are observed in the sample, filter
analyses. Soak the glassware in warm dilute (5 % v/v) reagent through a 0.45 µm, 0.8 µm, or 1.0 µm (nylon, TFE-
grade nitric acid for several hours, and then rinse thoroughly fluorocarbon, cellulose acetate/cellulose nitrate, or other com-
with deionized water. Xylene, kerosene, and other diluent patible material) membrane filter into an acid-cleaned con-
solvents used are incompatible with a variety of plastics. When tainer and retain the filtrate for analysis. Follow the same
possible, all plasticware should be replaced with FEP or PFA procedure for the blank solution used for the analysis of these
materials. samples.

X1.5 Do not use glassware or plasticware that has previ- X1.10 Testing should be performed under normal laboratory
ously contained solutions with high concentrations of the conditions using an operator with good experience in ICP-AES
element(s) of interest. technology.

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 D7111 − 16
X1.11 The instrument measurement capability is affected by calibration has changed. A check after every fifth sample or if
instrument maintenance quality, laboratory environment/ at least 30 min have elapsed from the time of the last analysis
protocols, equipment age, and other factors. is recommended. Recalibrate if the net intensity of the standard
changes by more than 5 % relative to previous check.
X1.12 Inspect the torch for cracks. Discard defective
torches. Use clean torches that do not have carbon deposits. X1.23 Low level working calibration standards should be
prepared fresh on the day of analysis from higher concentration
X1.13 Inspect the nebulizer tubing daily for kinks or cracks, (for example, 500 mg ⁄kg or 1000 mg ⁄kg) stock solution.
and replace if necessary. Measure the nebulizer uptake rate
daily to check for plugging. Clean it if the rate is not normal. X1.24 By experiment, determine the frequency of standards
preparation. Then, prepare fresh, as needed.
X1.14 Adjust the variations due to buildup of deposits on
the nebulizer during the course of determinations by frequently X1.25 When preparing multi-element standards, ensure that
nebulizing the check standard. the various reagents are mutually soluble in the solvent
employed, and do not form insoluble compounds by reacting
X1.15 When the carbon build-up in the torch is problematic, with each other. Stability of commercial standards is only
adjust the experimental conditions to eliminate the problem. applicable to the standard as provided. Once the standard is
Such adjustments can include: (1) reducing the sample intake diluted with a solvent, the stability is no longer assured by the
rate, (2) increasing the auxiliary argon gas flow rate, (3) using manufacturer.
a jacketed, chilled spray chamber, (4) lowering the torch
relative to the RF load coil, (5) diluting the sample, and (6) X1.26 Standard addition technique may be employed for
making other adjustments described in the instrument manual. samples known to have elemental or other interferences.
X1.16 The use of a variable speed peristaltic pump for X1.27 For best results, use a bracketing technique for
delivering sample solution to the nebulizer is highly recom- calibration. This involves measuring emission intensity read-
mended. The flow rate is typically in the range of 0.05 mL ⁄min ings for the calibration solutions before and after each of the
to 0.1 mL ⁄min. Inspect the peristaltic pump tubing daily, and sample solutions.
replace deteriorating tubing. Daily replacement is recom-
mended. X1.28 Verify the linearity of the concentrations/emission
response for each analyte following the instrument manufac-
X1.17 After initially igniting the plasma, allow the instru- turer’s instructions. Perform all determinations within this
ment to warm up to a minimum of 30 min. Some instrument concentration range. Prepare the standard solutions with con-
manufacturers recommend even longer warm-up periods to centrations at the top of the linear range. Match the matrix of
minimize changes in the slopes of calibration curves. During the standard solutions to sample solutions as closely as
this warm-up period, nebulize dilution solvent. possible. Keep all emission intensities within the linear and
calibration ranges. Dilute the sample solutions gravimetrically,
X1.18 Dilute the samples and calibration standards as much if necessary, with analyte-free solvents.
as possible to minimize nebulizer transport effects caused by
high viscosity samples, and to reduce potential spectral inter- X1.29 Before use, check the accuracy of element concen-
ferences. trations of commercially obtained calibration standards by
comparing against suitable primary standards, using alternative
X1.19 Always use a blank sample with all solvents and sources or analyzing by independent analytical methods.
other reagents added to the standards and the samples to check
for contamination. When blank values are significant, correct X1.30 Periodically, as needed determine the linearity of the
for the blank or select alternate reagents that give insignificant calibration curves. Perform quantitative analyses with linear
blank values. curves only.
X1.20 Use a blank and appropriate check standard after X1.31 The instrument shall be calibrated using a minimum
every fifth sample, or if at least 30 min have elapsed from the of three calibration standards and a calibration blank. The
time of last analysis. Recalibrate if the intensity of the standard calibration coefficient shall be equal or greater than 0.995.
changes by more than 5 % relative to the previous check. The
blank solution must contain all the reagents and be the same X1.32 Use the wavelengths specified in the test method for
volume as used in the processing of the samples. Carry the measurement, because they have been established by experi-
blank solution through the complete analytical procedure. ment and experience to be the optimum wavelengths, and free
from spectral interference.
X1.21 Standardize the instrument each time the plasma is
ignited. Carry out calibration prior to each group of samples to X1.33 Memory interferences result when higher levels of
be analyzed and after any change in instrumental conditions, as elements in a previous sample contribute to the signals
variation occurs in the instrument behavior. measured in a subsequently analyzed sample. Memory effects
can result from the buildup of sample material in the plasma
X1.22 A single check standard should be analyzed from torch and sample introduction system. To minimize memory
time to time during a series of samples to check whether the effects, allow sufficient solvent rinse time (not less than 60 s)

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 D7111 − 16
between the determinations. Memory effects are present if a tion. Avoid spectral interferences where possible by judicious
steady instead of an abrupt decrease in signal is observed from choice of wavelengths to be used or by comparing the results
taking multiple measurements. Additionally, blanks should be of two different wavelengths for the same element.
analyzed periodically to demonstrate freedom from memory
effects. The rinse times necessary for a particular element X1.39 With any instrument, the analyst must always be alert
should be estimated prior to analysis. Refer to the interferences to the possible presence of unexpected elements producing
section (Section 6) of this test method for further instructions. interfering spectral peaks.

X1.34 Differences in the viscosities of test specimen solu- X1.40 Internal standardization or the method of standard
tions and calibration standard solutions can cause differences in additions must be used to correct for instrumental drift as well
the uptake rates of if self-aspiration is used. These differences as suppressions or enhancements of instrument response
can adversely affect the accuracy of the analysis. These effects caused by the sample matrix. Internal standards should have
can be reduced by using a peristaltic pump to deliver solutions similar analytical behavior to the elements being determined.
to the nebulizer and by the use of internal standardization or X1.41 In choosing an internal standard, consider the purity
standard addition. Use of a peristaltic pump is strongly of (freedom from analyte), sensitivity, interferences, ionization
recommended to provide a constant flow of the solution. energies (that is, internal standard versus analyte), soluble/
compatible with sample matrix and coexistent species, etc.
X1.35 Particulates can plug the nebulizer thereby causing
low results. Also, the sample introduction system can limit the X1.42 If using the internal standard method, it is necessary
transport of particulates, and the plasma can incompletely to spike with the same amount of internal standard stock
atomize the particulates, thereby causing low results. Use of a solution as added to the samples.
concentric or alternatively a Babington-type high solids nebu-
lizer helps to minimize this effect. X1.43 High levels of dissolved solids in the sample may
contribute deposits of material on the nebulizer reducing the
X1.36 A mass flow controller to regulate the nebulizer gas effective diameter and shape of the orifice and, therefore, atom
may be used as recommended by the instrument manufacturer. transmission. Dissolved solid levels not exceeding 0.2 % (w/v)
are recommended to reduce such effects.
X1.37 At least three integrations of measurements should be
made for all samples (standards, blank, fuels) run. X1.44 Establish and implement a quality control protocol
that can aid in achieving the required data quality. It is strongly
X1.38 See the interferences section of the test method for recommended that a quality control sample be analyzed for
properly detecting and minimizing spectral interferences. every five or ten samples used in analysis. A control chart
Check for all spectral interferences expected from the elements should be plotted using the results and appropriate actions
present in the sample. Follow the manufacturer’s operating should be taken when the chart indicates out-of-statistical
guide to develop and apply correction factors to compensate control behavior. See Practice D6792 for guidance in this area.
for interferences. ICP spectrometer manufacturer’s software
may be used to provide corrections to interferences that cannot X1.45 Report results using the number of significant figures
be avoided by wavelength selection and background correc- specified in the test method standard.

X2. QUALITY CONTROL

X2.1 Confirm the performance of the instrument or the test may, but not necessarily, result in instrument re-calibration.
procedure by analyzing a QC sample.
X2.4 In the absence of explicit requirements given in the
X2.2 Prior to monitoring the measurement process, the user test method, the frequency of QC testing is dependent on the
of the test method needs to determine the average value and criticality of the quality being measured, the demonstrated
control limits of the QC sample. See Practice D6299 and MNL stability of the testing process, and customer requirements.
7.6 Generally, a QC sample is analyzed each testing day with
routine samples. The QC frequency should be increased if a
X2.3 Record the QC results and analyze by control charts or large number of samples are routinely analyzed. However,
other statistically equivalent techniques to ascertain the statis- when it is demonstrated that the testing is under statistical
tical control status of the total testing process. See Practice control, the QC testing frequency may be reduced. The QC
D6299, Practice D6792, and MNL 7.6 Investigate any out-of- sample precision should be checked against the ASTM test
control data for root cause(s). The results of this investigation method precision to ensure data quality.
X2.5 It is recommended that, if possible, the type of QC
6
ASTM Manual MNL 7, Manual on Presentation of Data Control Chart sample that is regularly tested be representative of the material
Analysis, 6th ed., ASTM International. routinely analyzed. An ample supply of QC sample material

10
 D7111 − 16
should be available for the intended period of use, and must be combination thereof, for further guidance on QC and control
homogenous and stable under the anticipated storage condi- charting techniques.
tions. See Practice D6299, Practice D6792, and MNL 7,6 or a

SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D7111 – 15a) that may impact the use of this standard. (Approved Dec. 1, 2016.)

(1) Added new Appendix X1 incorporating helpful hints to the

analyst using this test method.

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D7111 – 15) that may impact the use of this standard. (Approved July 1, 2015.)

(1) Revised subsection 15.3 by adding new subsection 15.3.1

and new Note 2.

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D7111 – 14) that may impact the use of this standard. (Approved April 1, 2015.)

(1) Updated reference to Military standard in 2.2; updated (3) Updated Table 1.
corresponding footnote. (4) Revised 7.2.
(2) Updated reference to Military standard in 5.2.

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