Professional Documents
Culture Documents
Standard Operation Protocol For ICP-MS Analysis TRACE Project
Standard Operation Protocol For ICP-MS Analysis TRACE Project
Standard Operation Protocol For ICP-MS Analysis TRACE Project
1. Scope
This document specifies a method for the determination of trace elements using
Inductively Coupled Plasma – Mass Spectrometry (ICP-MS).
The test solutions will be: simple solutions, such as water, digest liquors resulting
from the dissolution of samples into nitric acid or extractables from soils
The method has been validated for the determination of Al, As, Cd, Cr, Cu, Fe,
Hg, Pb, Mn, Ni, Se, Tl and Zn in various types of food, including composite diets,
cereals, rice, fish and offal by CSL. In the TRACE project however, it will be
applied to a greater range of elements, foodstuffs and sample types, but
appropriate care should be taken when interpreting the data.
For the TRACE project measurements the following element suite is required.
Element palette (31). The masses and calibration standards mentioned are for
guidance purposes only. (Merck VI refers to Merck VI Multi element standard,
Claritas refers to Spex Certiprep REE standard, Home made refers to single
element standard .
Notes have been included in this protocol (highlighted in italics), which are
intended to give additional information to the analyst, but which are not deemed
essential to the successful operation of the protocol. The protocol also describes
parameters used in the operation of key pieces of equipment, including power
settings, sample volumes, etc., However, laboratories using similar equipment,
but from a different manufacturer, should refer to their own instruments’ operating
instructions and manufacturers’ recommendations.
Information relating to the procedures preceding analysis of food-based samples
by ICP-MS, i.e., their dissolution into a suitable acid, etc., is given as an appendix
to this document but does not cover soil ‘extractables’. Also be aware that ISO
17294-1 and ISO 17294-2 have valuable suggestions on how to tune and
calibrate.
2. Principle
The resulting solutions will have been diluted with water, and internal standard (s)
added.
WARNING -The use of this method can involve hazardous materials, operations
and equipment. This document does not purport to address all the safety issues
associated with its use, especially HF. It is the responsibility of the user of this
method to establish appropriate health and safety practices.
3. Reagents
NOTE: The concentration of the trace elements in the reagents and water used shall be low
enough not to affect the result of the determination. Ideally, ultrapure water and high purity acids
and reagents (Ultrapure or equivalent grade) should be used. Redistillation of acids is also
acceptable.
NOTE: Sufficient reagents should be prepared to fully complete an analytical batch. New bottles
of reagents should not be started midway through an analytical batch.
Not less than 65% (mass fraction), with a density of approximately 1.4 kg L-1
3.2 Nitric acid (dilute, for preparation of standards, etc.) (Ultrapure -grade)
The concentration of the acid in this solution will be dependent on the final
dilution chosen for use with the digest solution, and should be calculated to match
it as closely as possible. In the examples given below, an assumption will be
made that the acid (in which the sample was digested) was transferred, diluted,
and made up to volume, 1:1 with water (3.5), giving a nitric acid concentration in
the digest solution of 32.5% (mass fraction).
Example 1. If the digest solution is subsequently diluted (1 + 4) with water (3.5),
the acid concentration in the resulting test solution will be approximately 6.5%
(mass fraction). Therefore, to prepare dilute nitric acid for use with the calibration
standards, a ratio of 1:10 (nitric acid: water) should be used, e.g., 100 ml of nitric
acid (3.1), made to volume (1000 ml) with water (3.5).
Example 2. If the digest solution requires a higher dilution (0.1 + 4.9) because of
the levels of dissolved solids, etc., the acid concentration in the resulting test
solution will be approximately 0.65% (mass fraction). Therefore, to prepare the
dilute nitric acid for use with the calibration standards, a ratio of 1:100 (nitric acid:
water) should be used, e.g., 10 ml of nitric acid (3.1), made to volume (1000 ml)
with water (3.5).
NOTE: If the digestion procedure included the use of hydrogen peroxide or hydrochloric acid, the
dilute nitric acid required for the preparation of the standards should also contain these chemicals
at an appropriate mass fraction. However, the analyst should be aware of the potential hazard
associated with the evolution of gases from solutions containing H2O2.
NOTE: If the digestion procedure included the use of hydrofluoric acid, the dilute nitric acid
required for the preparation of the standards should also contain this chemical at an appropriate
mass fraction. However, the analyst should be aware of the potential large hazards associated
with the use of HF. Only properly trained staff should be allowed to handle HF.
These can be prepared directly by dissolution of the metal or metal salt (traceable
to a NIST standard) in an appropriate acid solution. Prepared solutions are also
commercially available.
NOTE: If commercially prepared solutions are used, they should, where possible, be traceable to
a NIST standard or be suitably certified and should be Mass-Spec grade, i.e.¸ the quality of the
standards should reflect that they are going to be used in multi-element methods.
NOTE: Typical concentrations in the prepared stock solutions would be 1000 mg L-1 . However,
some may be higher or lower, so care should be taken to check the solution strength.
NOTE: If similar multi-elemental analyses are being performed on a routine basis, pre-prepared
multi-element solutions are commercially available from a number of suppliers, which can be
tailor-made to meet the specific needs of a particular matrix/analyte combination. However, QC
check solutions should be made from different stock standards to the calibration solutions. QC
solutions should be run after the calibration standards, at the end of the run and at regular
intervals throughout the run.
3.7.1 Example of standard solution preparation from the metal.
NOTE: Certain metals require dissolution in concentrated nitric acid, whilst other are best
dissolved in a diluted acid solution. Advice should be sought as to the appropriate method of
dissolution to be used.
NOTE: The following description is given only as an example. The actual volumes and
concentrations used will reflect what is required for the analysis of specific foods and also the
equipment/facilities available to the analyst.
Transfer 1 ml of the above solution to a volumetric flask (100 ml) and make up to
volume using dilute nitric acid (3.2). The resulting concentration of elements will
be: As and Se = 0.10 µg ml-1 and Al, Cd, Cr, Cu, Fe, Pb, Mn, Hg, Ni, Tl and Zn =
0.02 µg ml-1 .
3.7.2 Internal Standards
NOTE: Although a range of internal standards are suitable for use when
performing multi-element determinations for the TRACE project the elements
suggested to be used as internal standards are Ge, Rh or In, and Re or Pt. The
choice of internal standard (s) should be made, based on the following criteria:
Are they likely to occur naturally in the matrix (if so, choose an alternative).
Chemistry of analytes
− If using non-routine plasma conditions, e.g., reduced forward power, mixed
gases, etc, ensure that the internal standard exhibits similar ionisation behaviour
to that of the analyte.
NOTE: Ensure that the solutions are Mass-Spec grade, i.e.¸ the quality of the internal standards
should reflect that they are going to be used in multi-element methods.
NOTE: Monitor the response of the internal standard, to ensure that there are no significant
changes in its behaviour from sample to sample. If a significant difference, i.e., greater than 25%,
in the response obtained from a procedural blank and that from a sample, this should be taken as
an indication of matrix effect or interference/contamination, and would require further
investigation.
Possible ways of resolving this issue would be either to dilute the sample further, or to use a
Standard Addition Quantification procedure or Isotope Dilution MS.
An acid digest of a typical food matrix, which has been diluted in a similar way to
the test solutions.
The Optimisation Solution is suggested to contain Be, Mg, Cu, Rh, Ba, Ca, Ce,
Pb and U, at concentrations which produce count rates between 10,000 and
100,000 cps (this equates to between 1 and 10 ppb).
4. Apparatus and equipment
4.1 General
All glass and plastic ware should be cleaned and rinsed following the procedure
described in EN 13804:2002 or better.
4.3 Argon
4.4 ICP-MS
The instrument should be capable of measuring the mass range, from 5 to 250
amu, and should be fitted with a low-pulse peristaltic pump and autosampler
system.
NOTE: Given the presence of many of the target analytes in airborne particulate material,
consideration should be given to the use of a cover over the autosampler, to protect the samples
from contamination while they are awaiting analysis.
4.5 Cones
The material used in the construction of the cones should be compatible with the
analysis being performed, e.g. it may be beneficial to use platinum rather than
nickel cones when analysing for nickel.
5.1 General
NOTE: The basic steps in establishing stable and appropriate plasma will differ, depending on the
instrument’s manufacturer. What is described in this document is a guide to the operational
parameters that require attention if accurate and precise data is to be obtained.
Oxides <3%*
• NOTE: that a lower CeO/Ce ratio equates to improved matrix decomposition and more
consistent ionisation with changing matrix levels. For this reason, reducing the CeO/Ce ratio may
be considered a priority in normal system optimisation.
5.4 Operational parameters for data acquisition
Parameter Comment
Table 4 details interferences that can affect the 13-analyte elements covered by
this validated part of this protocol (Al, As, Cd, Cr, Cu, Fe, Hg, Pb, Mn, Ni, Se, Tl
and Zn). The analyst must take responsibility for identifying potential additional
interferences affecting the additional elements being analysed for TRACE, which
are not in this list.
NOTE: For many elements, there is more than one isotope available for quantitation. If possible, it
is advised that at least two isotopes are measured, allowing the ratio of the responses for the two
isotopes to be used as an indication that the quantifying isotope has been measured free from
chemical interference.
Note: Variation in the natural isotopic abundance of lead from different geographical locations
around the world is well documented. Therefore, to avoid any inaccuracy when quantifying lead, it
is common practice to add the 3 main isotopes of the element together, using a simple equation
embedded in the instrument method software.
5.6 Measurement
− A minimum of one (5-point) calibration curve at the start of the analytical run (a
second set of standards is advisable at the end of the run).
− QC check standards should immediately follow the analysis of the standard
calibration solutions, be dispersed randomly throughout the run (with no more
than 10 sample analyses between each check standard) and be measured at the
end of the run.
Note: The nebulisation of a number of ‘warm-up’ solutions, prior to the measurement of the
calibration standards should be considered, as this can assist in stabilising the interface region of
the ICP-MS.
5.7.1 General
− A value of at least 0.995 should be obtained from the regression fit for the
calibration standards.
− Ensure that variation in internal standard response does not vary by more than
25% between blank and sample solutions.
− Where multiple isotopic data has been obtained, the concentration calculated
on the individual isotopes should not vary by more than 10%.
All ICP-MS instruments have software that, if suitable information such as sample
weight is provided, can calculate the concentration of analyte in the original
sample. However, if this approach is not taken, the following manual calculation
procedure can be used to perform the calculation, assuming that there are no
concerns regarding chemical or isobaric interferences.
Calculate the content, w, as mass fraction of the element to be determined, in
milligram per kilogram of sample, using the following equation:
w = ( a – b) V
m
where
a is the concentration in the test solution, in milligrams per litre;
If (a-b) is lower than the sample solution detection limit (see 5.7.2), substitute (a-
b) with the value for the detection limit in the test solution for calculation of the
limit detection in the sample.
If required, recalculate the result to fresh weight if it is based on the dry matter
content of the sample. Give the result with an applicable number of significant
figures.
5.7.3 Calculation of the limits of detection and quantification
std dev blanks the standard deviation measured in at least three procedural
blanks V the dilution factor required to create the test solution M typical mass of
sample taken at the digestion stage, in grams.
Appendix A
Quality material and procedures associated with the TRACE ICP-MS analysis:
Each analytical batch should include sufficient QA and QC materials to allow the
accuracy of the data to be assessed, and to provide a means by which data can
be directly compared with that from another laboratory. It is suggested that each
batch should contain the following:
– Analytical batch
o A collection of test samples (or “unknowns”), certified reference
materials (CRMs), procedural blanks and spiked procedural blanks,
which have been analysed in such a way as to have a commonality
of;
– operator
o reagents (do not replenish reagents with fresh material from
different bottles, etc). environmental and instrumental conditions
– Unknowns
o Samples (or test materials) for which the elemental composition is
unknown
– Procedural blanks
o A solution, which is quantitatively representative of all of the
reagents used in the procedure, and which has been produced by
taking the reagents through all of the stages involved in the
procedure.
Within an analytical batch, the recovery of material from the ‘spike’ should fall
within the following bounds:
The recovery values for ALL the elements in a batch should be between 60 and
140%
The recovery values of 75% of the elements in a batch should be between 80 and
120%
The following CRM’s have been selected as suitable reference materials for the
TRACE project: NIST1548 “Typical Diet” which is to be measured with any batch
containing wheat, olives, olive oil, honey, lamb, beef or chicken. Additionally,
NIST1640 “Natural Water” is to be measured with the water samples, NIST1567a
“Wheat Flower” is to be measured with the wheat, NIST1547 “Peach leaves”
and/or BCR-062 “Olive leaves” is to be measured with the olives and olive oil,
NIST8414 “Muscle Tissue” is to be measured together with the meat samples.
In order to attain traceability of the results within the WP each partner must
ensure that with each measurement there must be a reference to the matching
reference material(s) measured in the same batch. In this manner any intra-lab
differences can be accounted for when integrating all data set for the
interpretation and model building. Additionally the performance on the quarterly
proficiency tests will be recorded on control charts for each lab and be available
form the TRACE intranet.