6020A

6020A
METHOD 6020A
INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY
SW-846 is not intended to be an analytical training manual. Therefore, method
procedures are written based on the assumption that they will be performed by analysts who are
formally trained in at least the basic principles of chemical analysis and in the use of the subject
technology.
In addition, SW-846 methods, with the exception of required method use for the analysis
of method-defined parameters, are intended to be guidance methods which contain general
information on how to perform an analytical procedure or technique which a laboratory can use
as a basic starting point for generating its own detailed Standard Operating Procedure (SOP),
either for its own general use or for a specific project application. The performance data
included in this method are for guidance purposes only, and are not intended to be and must
not be used as absolute QC acceptance criteria for purposes of laboratory accreditation.
1.0
SCOPE AND APPLICATION
1.1
Inductively coupled plasma-mass spectrometry (ICP-MS) is applicable to the
determination of sub-µg/L concentrations of a large number of elements in water samples and in
waste extracts or digests (Refs. 1 and 2). When dissolved constituents are required, samples
must be filtered and acid-preserved prior to analysis. No digestion is required prior to analysis
for dissolved elements in water samples. Acid digestion prior to filtration and analysis is
required for groundwater, aqueous samples, industrial wastes, soils, sludges, sediments, and
other solid wastes for which total (acid-soluble) elements are required.
1.2
ICP-MS has been applied to the determination of over 60 elements in various
matrices. Analytes for which EPA has demonstrated the acceptability of this method in a multilaboratory study on solid and aqueous wastes are listed below.
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
CASRNa
7429-90-5
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-70-2
7440-47-3
7440-48-4
7440-50-8
7439-89-6
7439-92-1
7439-95-4
7439-96-5
7439-97-6
7440-02-0
(Al)
(Sb)
(As)
(Ba)
(Be)
(Cd)
(Ca)
(Cr)
(Co)
(Cu)
(Fe)
(Pb)
(Mg)
(Mn)
(Hg)
(Ni)
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Element
CASRNa
Potassium
(K)
7440-09-7
Selenium
(Se)
7782-49-2
Silver
(Ag)
7440-22-4
Sodium
(Na)
7440-23-5
Thallium
(Tl)
7440-28-0
Vanadium
(V)
7440-62-2
Zinc
(Zn)
7440-66-6
a
Chemical Abstract Service Registry Number
Acceptability of this method for an element was based upon the multi-laboratory
performance compared with that of either furnace atomic absorption spectrophotometry or
inductively coupled plasma-atomic emission spectrometry. It should be noted that one multilaboratory study was conducted in 1988 and advances in ICP-MS instrumentation and software
have been made since that time and additional studies have been added with validation and
improvements in performance of the method. Performance, in general, exceeds the multilaboratory performance data for the listed elements. It is expected that current performance will
exceed the multi-laboratory performance data for the listed elements (and others) that are
provided in Sec. 13.0. The lower limit of quantitation and linear ranges will vary with the
matrices, instrumentation, and operating conditions. In relatively simple matrices, quantitation
limits will generally be below 0.1 µg/L. Less sensitive elements (like Se and As) and
desensitized major elements may be 1.0 µg/L or higher.
1.3
If this method is used to determine any analyte not listed in Sec. 1.2, it is the
responsibility of the analyst to demonstrate the accuracy and precision of the method in the
waste to be analyzed. The analyst is always required to monitor potential sources of
interferences and take appropriate action to ensure data of known quality (see Sec. 9.0). Other
elements and matrices may be analyzed by this method if performance is demonstrated for the
analyte of interest, in the matrices of interest, at the concentration levels of interest in the same
manner as the listed elements and matrices (see Sec. 9.0).
1.4
An appropriate internal standard is required for each analyte determined by ICPMS. Recommended internal standards are 6Li, 45Sc, 89Y, 103Rh, 115In, 159Tb, 165Ho, 74Ge, and
209
Bi. The lithium internal standard should have an enriched abundance of 6Li, so that
interference from lithium native to the sample is minimized. Other elements may need to be
used as internal standards when samples contain significant native amounts of the
recommended internal standards.
1.5
Prior to employing this method, analysts are advised to consult the each
preparative method that may be employed in the overall analysis (e.g., a 3000 series method)
for additional information on quality control procedures, development of QC acceptance criteria,
calculations, and general guidance. Analysts also should consult the disclaimer statement at
the front of the manual and the information in Chapter Two for guidance on the intended
flexibility in the choice of methods, apparatus, materials, reagents, and supplies, and on the
responsibilities of the analyst for demonstrating that the techniques employed are appropriate
for the analytes of interest, in the matrix of interest, and at the levels of concern.
In addition, analysts and data users are advised that, except where explicitly specified in a
regulation, the use of SW-846 methods is not mandatory in response to Federal testing
requirements. The information contained in this method is provided by EPA as guidance to be
used by the analyst and the regulated community in making judgments necessary to generate
results that meet the data quality objectives for the intended application.
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1.6
Use of this method is restricted to use by, or under supervision of, properly
experienced and trained personnel, including spectroscopists who are knowledgeable in the
recognition and in the correction of spectral, chemical, and physical interferences in ICP-MS.
Each analyst must demonstrate the ability to generate acceptable results with this method.
2.0
SUMMARY OF METHOD
2.1
Prior to analysis, samples should be solubilized or digested using the appropriate
sample preparation methods (see Chapter Three). When analyzing groundwater or other
aqueous samples for dissolved constituents, acid digestion is not necessary if the samples are
filtered and acid preserved prior to analysis (refer to Sec. 1.1).
2.2
This method describes the multi-elemental determination of analytes by ICP-MS in
environmental samples. The method measures ions produced by a radio-frequency inductively
coupled plasma. Analyte species originating in a liquid are nebulized and the resulting aerosol
is transported by argon gas into the plasma torch. The ions produced by high temperatures are
entrained in the plasma gas and extracted through a differentially pumped vacuum interface and
separated on the basis of their mass-to-charge ratio by a mass spectrometer. The ions
transmitted through the mass spectrometer are quantified by a channel electron multiplier or
Faraday detector and the ion information is processed by the instrument’s data handling
system. Interferences must be assessed and valid corrections applied or the data qualified to
indicate problems. Interference correction must include compensation for background ions
contributed by the plasma gas, reagents, and constituents of the sample matrix.
3.0
DEFINITIONS
Refer to Chapter One, Chapter Three, and the manufacturer's instructions for definitions
that may be applicable to this procedure.
4.0
INTERFERENCES
4.1
Solvents, reagents, glassware, and other sample processing hardware may
yield artifacts and/or interferences to sample analysis. All these materials must be
demonstrated to be free from interferences under the conditions of the analysis by analyzing
method blanks. Specific selection of reagents and purification of solvents by distillation in
all-glass systems may be necessary. Refer to each method to be used for specific guidance on
quality control procedures and to Chapter Three for general guidance on the cleaning of
glassware. Also refer to the preparative methods to be used for discussions on interferences.
4.2
Isobaric elemental interferences in ICP-MS are caused by isotopes of different
elements forming atomic ions with the same nominal mass-to-charge ratio (m/z). A data system
must be used to correct for these interferences. This involves determining the signal for another
isotope of the interfering element and subtracting the appropriate signal from the analyte
isotope signal. Since commercial ICP-MS instruments nominally provide unit resolution at 10%
of the peak height, very high ion currents at adjacent masses can also contribute to ion signals
at the mass of interest. Although this type of interference is uncommon, it is not easily
corrected, and samples exhibiting a significant problem of this type could require resolution
improvement, matrix separation, or analysis using another verified and documented isotope, or
use of another method.
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4.3
Isobaric molecular and doubly-charged ion interferences in ICP-MS are caused by
ions consisting of more than one atom or charge, respectively. Most isobaric interferences that
could affect ICP-MS determinations have been identified in the literature (Refs. 3 and 4).
Examples include 75ArCl+ ion on the 75As signal and MoO+ ions on the cadmium isotopes. While
the approach used to correct for molecular isobaric interferences is demonstrated below using
the natural isotope abundances from the literature (Ref. 5), the most precise coefficients for an
instrument can be determined from the ratio of the net isotope signals observed for a standard
solution at a concentration providing suitable (<1%) counting statistics. Because the 35Cl natural
abundance of 75.77% is 3.13 times the 37Cl abundance of 24.23%, the chloride correction for
arsenic can be calculated (approximately) as follows (where the 38Ar37Cl+ contribution at m/z 75
is a negligible 0.06% of the 40Ar35Cl+ signal):
Corrected arsenic signal (using natural isotopes abundances for coefficient approximations) =
(m/z 75 signal) - (3.13) (m/z 77 signal) + (2.73) (m/z 82 signal),
where the final term adjusts for any selenium contribution at 77 m/z.
NOTE:
Arsenic values can be biased high by this type of equation when the net signal at m/z
82 is caused by ions other than 82Se+, (e.g., 81BrH+ from bromine wastes [Ref. 6]).
Similarly:
Corrected cadmium signal (using natural isotopes abundances for coefficient approximations) =
(m/z 114 signal) - (0.027)(m/z 118 signal) - (1.63)(m/z 108 signal),
where last 2 terms adjust for any 114Sn+ or 114MoO+ contributions at m/z 114.
NOTE:
Cadmium values will be biased low by this type of equation when 92ZrO+ ions
contribute at m/z 108, but use of m/z 111 for Cd is even subject to direct (94ZrOH+) and
indirect (90ZrO+) additive interferences when Zr is present.
NOTE:
As for the arsenic equation above, the coefficients could be improved. The most
appropriate coefficients for a particular instrument can be determined from the ratio of
the net isotope signals observed for a standard solution at a concentration providing
suitable (<1%) counting precision.
The accuracy of these types of equations is based upon the constancy of the observed
isotopic ratios for the interfering species. Corrections that presume a constant fraction of a
molecular ion relative to the "parent" ion have not been found (Ref. 7) to be reliable, e.g., oxide
levels can vary with operating conditions. If a correction for an oxide ion is based upon the ratio
of parent-to-oxide ion intensities, the correction must be adjusted for the degree of oxide
formation by the use of an appropriate oxide internal standard previously demonstrated to form
a similar level of oxide as the interferent. For example, this type of correction has been
reported (Ref. 7) for oxide-ion corrections using ThO+/Th+ for the determination of rare earth
elements. The use of aerosol desolvation and/or mixed gas plasmas have been shown to
greatly reduce molecular interferences (Ref. 8). These techniques can be used provided that
the lower limits of quantitation, accuracy, and precision requirements for analysis of the samples
can be met.
4.4
Additionally, solid phase chelation may be used to eliminate isobaric interferences
from both element and molecular sources. An on-line method has been demonstrated for
environmental waters such as sea water, drinking water and acid decomposed samples. Acid
decomposed samples refer to samples decomposed by methods similar to Methods 3052,
3051, 3050 or 3015. Samples with percent levels of iron and aluminum should be avoided. The
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method also provides a method for preconcentration to enhance quantitation limits
simultaneously with elimination of isobaric interferences. The method relies on chelating resins
such as imminodiacetate or other appropriate resins and selectively concentrates the elements
of interest while eliminating interfering elements from the sample matrix. By eliminating the
elements that are direct isobaric interferences or those that form isobaric interfering molecular
masses, the mass region is simplified and these interferences can not occur. The method has
been proven effective for the certification of standard reference materials and validated using
SRMs (Refs. 13 through 15). The method has the potential to be used on-line or off-line as an
effective sample preparation method specifically designed to address interference problems.
4.5
Physical interferences are associated with the sample nebulization and transport
processes as well as with ion-transmission efficiencies. Nebulization and transport processes
can be affected if a matrix component causes a change in surface tension or viscosity.
Changes in matrix composition can cause significant signal suppression or enhancement (Ref.
9). Dissolved solids can deposit on the nebulizer tip of a pneumatic nebulizer and on the
interface skimmers (reducing the orifice size and the instrument performance). Total solid
levels below 0.2% (2,000 mg/L) are recommended (Ref. 10) to minimize solid deposition. An
internal standard can be used to correct for physical interferences, if it is carefully matched to
the analyte so that the two elements are similarly affected by matrix changes (Ref. 11). When
intolerable physical interferences are present in a sample, a significant suppression of the
internal standard signals (to less than 30% of the signals in the calibrations standard) will be
observed. Dilution of the sample fivefold (1+4) will usually eliminate the problem (see Sec. 9.5).
4.6
Memory interferences or carry-over can occur when there are large concentration
differences between samples or standards which are analyzed sequentially. Sample deposition
on the sampler and skimmer cones, spray chamber design, and the type of nebulizer affect the
extent of observed memory interferences. The rinse period between samples must be long
enough to eliminate significant memory interference.
5.0
SAFETY
5.1
This method does not address all safety issues associated with its use. The
laboratory is responsible for maintaining a safe work environment and a current awareness file
of OSHA regulations regarding the safe handling of the chemicals specified in this method. A
reference file of material safety data sheets (MSDSs) should be available to all personnel
involved in these analyses.
5.2
Concentrated nitric and hydrochloric acids are moderately toxic and extremely
irritating to skin and mucus membranes. Use these reagents in a hood and if eye or skin
contact occurs, flush with large volumes of water. Always wear safety glasses or a shield for
eye protection when working with these reagents. Hydrofluoric acid is a very toxic acid and
penetrates the skin and tissues deeply if not treated immediately. Injury occurs in two stages;
first, by hydration that induces tissue necrosis and then by penetration of fluoride ions deep into
the tissue and by reaction with calcium. Boric acid and other complexing reagents and
appropriate treatment agents should be administered immediately. Consult appropriate safety
literature and have the appropriate treatment materials readily available prior to working with
this acid. See Method 3052 for specific suggestions for handling hydrofluoric acid from a safety
and an instrument standpoint.
5.3
Many metal salts are extremely toxic if inhaled or swallowed. Extreme care must
be taken to ensure that samples and standards are handled properly and that all exhaust gases
are properly vented. Wash hands thoroughly after handling.
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5.4
The acidification of samples containing reactive materials may result in the release
of toxic gases, such as cyanides or sulfides. For this reason, the acidification and digestion of
samples should be performed in an approved fume hood.
6.0
EQUIPMENT AND SUPPLIES
6.1
Inductively coupled plasma-mass spectrometer -- A system capable of providing
resolution, better than or equal to 1.0 amu at 10% peak height is required. The system must
have a mass range from at least 6 to 240 amu and a data system that allows corrections for
isobaric interferences and the application of the internal standard technique. Use of a
mass-flow controller for the nebulizer argon and a peristaltic pump for the sample solution is
recommended.
6.2
7.0
Argon gas supply -- High-purity grade (99.99%).
REAGENTS AND STANDARDS
7.1
Reagent- or trace metals-grade chemicals must be used in all tests. Unless
otherwise indicated, it is intended that all reagents conform to the specifications of the
Committee on Analytical Reagents of the American Chemical Society, where such
specifications are available. Other grades may be used, provided it is first ascertained that the
reagent is of sufficiently high purity to permit its use without lessening the accuracy of the
determination.
7.2
Acids used in the preparation of standards and for sample processing must be of
high purity. Redistilled acids are recommended because of the high sensitivity of ICP-MS.
Nitric acid at less than 2% (v/v) is required for ICP-MS to minimize damage to the interface and
to minimize isobaric molecular-ion interferences with the analytes. Many more molecular-ion
interferences are observed when hydrochloric and sulfuric acids are used (Refs. 3 and 4).
Concentrations of antimony and silver between 50-500 µg/L require 1% (v/v) HCl for stability; for
concentrations above 500 µg/L Ag, additional HCl will be needed. Consequently, accuracy of
analytes requiring significant chloride molecular ion corrections (such as As and V) will degrade.
7.3
Reagent water -- All references to water in the method refer to reagent water,
unless otherwise specified. Reagent water must be free of interferences.
7.4
Standard stock solutions for each analyte may be purchased or prepared from
ultra-high purity grade chemicals or metals (99.99 or greater purity). See Method 6010 for
instructions on preparing standard solutions from solids.
7.4.1
Bismuth internal standard stock solution (1 mL = 100 µg of Bi) -- Dissolve
0.1115 g of Bi2O3 in a minimum amount of dilute HNO3. Add 10 mL of conc. HNO3 and
dilute to 1,000 mL with reagent water.
7.4.2
Germanium internal standard stock solution (1 mL = 100 µg of Ge) -Dissolve 0.2954 g of GeCl4 in a minimum amount of dilute HNO3. Add 10 mL of conc.
HNO3 and dilute to 1,000 mL with reagent water.
7.4.3
Holmium internal standard stock solution (1 mL = 100 µg of Ho) -Dissolve 0.1757 g of Ho2(CO3)2C5H2O in 10 mL of reagent water and 10 mL of HNO3. After
dissolution is complete, warm the solution to degas. Add 10 mL conc. of HNO3 and dilute
to 1,000 mL with reagent water.
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7.4.4
Indium internal standard stock solution (1 mL = 100 µg of In) -- Dissolve
0.1000 g of indium metal in 10 mL of conc. HNO3. Dilute to 1,000 mL with reagent water.
7.4.5
Lithium internal standard stock solution (1 mL = 100 µg of 6Li) -- Dissolve
0.6312 g of 95-atom-% 6Li, Li2CO3 in 10 mL of reagent water and 10 mL of HNO3. After
dissolution is complete, warm the solution to degas. Add 10 mL conc. of HNO3 and dilute
to 1,000 mL with reagent water.
7.4.6
Rhodium internal standard stock solution (1 mL = 100 µg of Rh) -Dissolve 0.3593 g of ammonium hexachlororhodate (III) (NH4)3RhCl6 in 10 mL reagent
water. Add 100 mL of conc. HCl and dilute to 1,000 mL with reagent water.
7.4.7
Scandium internal standard stock solution (1 mL = 100 µg of Sc) -Dissolve 0.15343 g of Sc2O3 in 10 mL (1+1) of hot HNO3. Add 5 mL of conc. HNO3 and
dilute to 1,000 mL with reagent water.
7.4.8
Terbium internal standard stock solution (1 mL = 100 µg of Tb) -- Dissolve
0.1828 g of Tb2(CO3)3C5H2O in 10 mL (1+1) of HNO3. After dissolution is complete, warm
the solution to degas. Add 5 mL of conc. HNO3 and dilute to 1,000 mL with reagent water.
7.4.9
Yttrium internal standard stock solution (1 mL = 100 µg of Y) -- Dissolve
0.2316 g of Y2(CO3)3C3H2O in 10 mL (1+1) of HNO3. Add 5 mL conc. of HNO3 and dilute to
1,000 mL with reagent water.
7.4.10 Titanium interference stock solution (1 mL = 100 µg of Ti) -- Dissolve
0.4133 g of (NH4)2TiF6 in reagent water. Add 2 drops of conc. HF and dilute to 1,000 mL
with reagent water.
7.4.11 Molybdenum interference stock solution (1 mL = 100 µg of Mo) -Dissolve 0.2043 g of (NH4)2MoO4 in reagent water. Dilute to 1,000 mL with reagent water.
7.4.12
Gold preservative stock solution for mercury (1 mL = 100 µg) -Recommend purchasing as high purity prepared solution of AuCl3 in dilute hydrochloric
acid matrix.
7.5
Mixed calibration standard solutions are prepared by diluting the stock-standard
solutions to levels in the linear range for the instrument in a solvent consisting of 1% (v/v) HNO3
in reagent water. The calibration standard solutions must contain a suitable concentration of an
appropriate internal standard for each analyte. Internal standards may be added on-line at the
time of analysis using a second channel of the peristaltic pump and an appropriate mixing
manifold. Generally, an internal standard should be no more than 50 amu removed from the
analyte. Recommended internal standards include 6Li, 45Sc, 89Y, 103Rh, 115In, 159Tb, 169Ho, 74Ge
and 209Bi. Prior to preparing the mixed standards, each stock solution must be analyzed
separately to determine possible spectral interferences or the presence of impurities. Care
must be taken when preparing the mixed standards to ensure that the elements are compatible
and stable together. Transfer the mixed standard solutions to freshly acid-cleaned FEP
fluorocarbon or previously unused polyethylene or polypropylene bottles for storage. For all
intermediate and working standards, especially low level standards (i.e., <1 ppm), stability must
be demonstrated prior to use. Fresh mixed standards must be prepared as needed with the
realization that concentrations can change on aging. (Refer to Sec. 10.3.1 for guidance on
determining the viability of standards.)
7.6
Blanks -- Three types of blanks are required for the analysis. The calibration
blank is used in establishing the calibration curve. The method blank is used to monitor for
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possible contamination resulting from either the reagents (acids) or the equipment used during
sample processing including filtration. The rinse blank is used to flush the system between all
samples and standards.
7.6.1
The calibration blank consists of the same concentration(s) of the same
acid(s) used to prepare the final dilution of the calibrating solutions of the analytes [often
1% HNO3 (v/v) in reagent water] along with the selected concentrations of internal
standards such that there is an appropriate internal standard element for each of the
analytes. Use of HCl for antimony and silver is cited in Sec. 7.2.
7.6.2
The method blank must contain all of the reagents in the same volumes
as used in the processing of the samples. The method blank must be carried through the
complete procedure and contain the same acid concentration in the final solution as the
sample solution used for analysis (refer to Sec. 9.9).
7.6.3
The rinse blank consists of 1 to 2% of HNO3 (v/v) in reagent water.
Prepare a sufficient quantity to flush the system between standards and samples. If
mercury is to be analyzed, the rinse blank should also contain 2 µg/mL (ppm) of AuCl3
solution.
7.7
The interference check solution (ICS) is prepared to contain known concentrations
of interfering elements that will demonstrate the magnitude of interferences and provide an
adequate test of any corrections. Chloride in the ICS provides a means to evaluate software
corrections for chloride-related interferences such as 35Cl16O+ on 51V+ and 40Ar35Cl+ on 75As+.
Iron is used to demonstrate adequate resolution of the spectrometer for the determination of
manganese. Molybdenum serves to indicate oxide effects on cadmium isotopes. The other
components are present to evaluate the ability of the measurement system to correct for various
molecular-ion isobaric interferences. The ICS is used to verify that the interference levels are
corrected by the data system within quality control limits.
NOTE:
The final ICS solution concentrations in Table 1 are intended to evaluate corrections
for known interferences on only the analytes in Sec. 1.2. If this method is used to
determine an element not listed in Sec. 1.2, the analyst should modify the ICS
solutions, or prepare an alternative ICS solution, to allow adequate verification of
correction of interferences on the unlisted element (see Sec. 9.7).
7.7.1
These solutions must be prepared from ultra-pure reagents. They can be
obtained commercially or prepared by the following procedure.
7.7.1.1
Mixed ICS solution I may be prepared by adding 13.903 g of
Al(NO3)3C9H2O, 2.498 g of CaCO3 (dried at 180 EC for 1 hr before weighing),
1.000 g of Fe, 1.658 g of MgO, 2.305 g of Na2CO3, and 1.767 g of K2CO3 to 25 mL
of reagent water. Slowly add 40 mL of (1+1) HNO3. After dissolution is complete,
warm the solution to degas. Cool and dilute to 1,000 mL with reagent water.
7.7.1.2
Mixed ICS solution II may be prepared by slowly adding
7.444 g of 85 % H3PO4, 6.373 g of 96% H2SO4, 40.024 g of 37% HCl, and 10.664 g
of citric acid C6O7H8 to 100 mL of reagent water. Dilute to 1,000 mL with reagent
water.
7.7.1.3
Mixed ICS solution III may be prepared by adding 1.00 mL
each of 100-µg/mL arsenic, cadmium, selenium, chromium, cobalt, copper,
manganese, nickel, silver, vanadium, and zinc stock solutions to about 50 mL of
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reagent water. Add 2.0 mL of concentrated HNO3, and dilute to 100.0 mL with
reagent water.
7.7.1.4
Working ICS solutions
7.7.1.4.1
ICS-A may be prepared by adding 10.0 mL of
mixed ICS solution I (Sec. 7.7.1.1), 2.0 mL each of 100-µg/mL titanium
stock solution (Sec. 7.4.9) and molybdenum stock solution (Sec. 7.4.10),
and 5.0 mL of mixed ICS solution II (Sec. 7.7.1.2). Dilute to 100 mL with
reagent water. ICS solution A must be prepared fresh weekly.
7.7.1.4.2
ICS-AB may be prepared by adding 10.0 mL of
mixed ICS solution I (Sec. 7.7.1.1), 2.0 mL each of 100-µg/mL titanium
stock solution (Sec. 7.4.9) and molybdenum stock solution (Sec. 7.4.10),
5.0 mL of mixed ICS solution II (Sec. 7.7.1.2), and 2.0 mL of mixed ICS
solution III (Sec. 7.7.1.3). Dilute to 100 mL with reagent water. Although
the ICS solution AB must be prepared fresh weekly, the analyst should be
aware that the solution may precipitate silver more quickly.
7.8
The initial calibration verification (ICV) standard is prepared by the analyst (or a
purchased second source reference material) by combining compatible elements from a
standard source different from that of the calibration standard, and at concentration near the
midpoint of the calibration curve (see Sec. 10.4.3 for use). This standard may also be
purchased.
7.9
The continuing calibration verification (CCV) standard should be prepared in the
same acid matrix using the same standards used for calibration, at a concentration near the
mid-point of the calibration curve (see Sec. 10.4.4 for use).
7.10 Mass spectrometer tuning solution. A solution containing elements representing all
of the mass regions of interest (for example, 10 µg/L of Li, Co, In, and Tl) must be prepared to
verify that the resolution and mass calibration of the instrument are within the required
specifications (see Sec. 10.2). This solution is also used to verify that the instrument has
reached thermal stability (see Sec. 11.4).
8.0
SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1
See the introductory material in Chapter Three, "Inorganic Analytes."
8.2
Only polyethylene or fluorocarbon (TFE or PFA) containers are recommended for
use in this method.
9.0
QUALITY CONTROL
9.1
Refer to Chapter One for additional guidance on quality assurance (QA) and
quality control (QC) protocols. When inconsistencies exist between QC guidelines, methodspecific QC criteria take precedence over both technique-specific criteria and those criteria
given in Chapter One, and technique-specific QC criteria take precedence over the criteria in
Chapter One. Any effort involving the collection of analytical data should include development
of a structured and systematic planning document, such as a Quality Assurance Project Plan
(QAPP) or a Sampling and Analysis Plan (SAP), which translates project objectives and
specifications into directions for those that will implement the project and assess the results.
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Each laboratory should maintain a formal quality assurance program. The laboratory should
also maintain records to document the quality of the data generated. All data sheets and
quality control data should be maintained for reference or inspection.
9.2
Refer to a 3000 series method (Method 3005, 3010, 3015, 3031, 3040, 3050,
3051, or 3052) for appropriate QC procedures to ensure the proper operation of the various
sample preparation techniques.
9.3
Instrument detection limits (IDLs) are a useful tool to evaluate the instrument noise
level and response changes over time for each analyte from a series of reagent blank analyses
to obtain a calculated concentration. They are not to be confused with the lower limits of
quantitation, nor should they be used in establishing this limit. It may be helpful to compare the
calculated IDLs to the established lower limit of quantitation, however, it should be understood
that the lower limit of quantitation needs to be verified according to the guidance in Sec. 10.2.3.
IDLs in µg/L can be estimated by calculating the average of the standard deviations of
three runs on three non-consecutive days from the analysis of a reagent blank solution with
seven consecutive measurements per day. Each measurement should be performed as though
it were a separate analytical sample (i.e., each measurement must be followed by a rinse and/or
any other procedure normally performed between the analysis of separate samples). IDLs
should be determined at least every three months or at a project-specific designated frequency
and kept with the instrument log book. Refer to Chapter One for additional guidance.
9.4
Initial demonstration of proficiency
Each laboratory must demonstrate initial proficiency with each sample preparation (a 3000
series method) and determinative method combination it utilizes by generating data of
acceptable accuracy and precision for target analytes in a clean matrix. If an autosampler is
used to perform sample dilutions, before using the autosampler to dilute samples, the laboratory
should satisfy itself that those dilutions are of equivalent or better accuracy than is achieved by
an experienced analyst performing manual dilutions. The laboratory must also repeat the
demonstration of proficiency whenever new staff members are trained or significant changes in
instrumentation are made.
9.5
Dilute and reanalyze samples that exceed the linear dynamic range or use an
alternate, less sensitive calibration for which quality control data are already established.
9.6
The intensities of all internal standards must be monitored for every analysis. If
the intensity of any internal standard in a sample falls below 70% of the intensity of that internal
standard in the initial calibration standard, a significant matrix effect must be suspected. As an
example, if the initial calibration internal standard response is 100,000 cps, anything below
70,000 cps in the sample would be unacceptable. Under these conditions, the established
lower limit of quantitation has degraded and the correction ability of the internal standardization
technique becomes questionable. The following procedure is followed -- First, make sure the
instrument has not drifted by observing the internal standard intensities in the nearest clean
matrix (calibration blank, Sec. 7.6.1). If the low internal standard intensities are also seen in the
nearest calibration blank, terminate the analysis, correct the problem, recalibrate, verify the new
calibration, and reanalyze the affected samples. If drift has not occurred, matrix effects need to
be removed by dilution of the affected sample. The sample must be diluted fivefold (1+4) and
reanalyzed with the addition of appropriate amounts of internal standards. If the first dilution
does not eliminate the problem, this procedure must be repeated until the internal-standard
intensities rise to the minimum 70% limit. Reported results must be corrected for all dilutions.
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9.7
To obtain analyte data of known quality, it is necessary to measure more than the
analytes of interest in order to apply corrections or to determine whether interference
corrections are necessary. For example, tungsten oxide moleculars can be very difficult to
distinguish from mercury isotopes. If the concentrations of interference sources (such as C, Cl,
Mo, Zr, W) are such that, at the correction factor, the analyte is less than the limit of
quantification and the concentration of interferents are insignificant, then the data may go
uncorrected. Note that monitoring the interference sources does not necessarily require
monitoring the interferant itself, but that a molecular species may be monitored to indicate the
presence of the interferent. When correction equations are used, all QC criteria must also be
met. Extensive QC for interference corrections are required at all times. The monitored masses
must include those elements whose hydrogen, oxygen, hydroxyl, chlorine, nitrogen, carbon and
sulfur molecular ions could impact the analytes of interest. Unsuspected interferences may be
detected by adding pure major matrix components to a sample to observe any impact on the
analyte signals. When an interference source is present, the sample elements impacted must
be flagged to indicate (a) the percentage interference correction applied to the data or (b) an
uncorrected interference by virtue of the elemental equation used for quantitation. The isotope
proportions for an element or molecular-ion cluster provide information useful for quality
assurance.
NOTE:
Only isobaric elemental, molecular, and doubly charged interference corrections
which use the observed isotopic-response ratios or parent-to-oxide ratios (provided
an oxide internal standard is used as described in Sec. 4.2) for each instrument
system are acceptable corrections for use in Method 6020.
9.8
For each batch of samples processed, at least one method blank must be carried
throughout the entire sample preparation and analytical process, as described in Chapter One.
A method blank is prepared by using a volume or weight of reagent water at the volume or
weight specified in the preparation method, and then carried through the appropriate steps of
the analytical process. These steps may include, but are not limited to, prefiltering, digestion,
dilution, filtering, and analysis. If the method blank does not contain target analytes at a level
that interferes with the project-specific DQOs, then the method blank would be considered
acceptable.
In the absence of project-specific DQOs, if the blank is less than 10% of the lower limit of
quantitation check sample concentration, less than 10% of the regulatory limit, or less than 10%
of the lowest sample concentration for each analyte in a given preparation batch, whichever is
greater, then the method blank is considered acceptable. If the method blank cannot be
considered acceptable, the method blank should be re-run once, and if still unacceptable, then
all samples after the last acceptable method blank should be reprepared and reanalyzed along
with the other appropriate batch QC samples. These blanks will be useful in determining if
samples are being contaminated. If the method blank exceeds the criteria, but the samples are
all either below the reporting level or below the applicable action level or other DQOs, then the
sample data may be used despite the contamination of the method blank.
9.9
Laboratory control sample (LCS)
For each batch of samples processed, at least one LCS must be carried throughout the
entire sample preparation and analytical process. The laboratory control samples should be
spiked with each analyte of interest at the project-specific action level or, when lacking projectspecific action levels, at approximately mid-point of the linear dynamic range. Acceptance
criteria should either be defined in the project-specifc planning documents or set at a laboratory
derived limit developed through the use of historical analyses. In the absence of project-specific
or historical data generated criteria, this limit should be set at ± 20% of the spiked value.
Acceptance limits derived from historical data should be no wider that ± 20%. If the laboratory
control sample is not acceptable, then the laboratory control sample should be re-run once and,
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if still unacceptable, all samples after the last acceptable laboratory control sample should be
reprepared and reanalyzed.
Concurrent analyses of standard reference materials (SRMs) containing known amounts
of analytes in the media of interest are recommended and may be used as an LCS. For solid
SRMs, 80 - 120% accuracy may not be achievable and the manufacturer’s established
acceptance criterion should be used for soil SRMs.
9.10
Matrix spike, unspiked duplicate, or matrix spike duplicate (MS/Dup or MS/MSD)
Documenting the effect of the matrix, for a given preparation batch consisting of similar
sample characteristics, should include the analysis of at least one matrix spike and one
duplicate unspiked sample or one matrix spike/matrix spike duplicate pair. The decision on
whether to prepare and analyze duplicate samples or a matrix spike/matrix spike duplicate must
be based on a knowledge of the samples in the sample batch or as noted in the project-specific
planning documents. If samples are expected to contain target analytes, then laboratories may
use one matrix spike and a duplicate analysis of an unspiked field sample. If samples are not
expected to contain target analytes, laboratories should use a matrix spike and matrix spike
duplicate pair.
For each batch of samples processed, at least one MS/Dup or MS/MSD sample set should
be carried throughout the entire sample preparation and analytical process as described in
Chapter One. MS/MSDs are intralaboratory split samples spiked with identical concentrations
of each analyte of interest. The spiking occurs prior to sample preparation and analysis. An
MS/Dup or MS/MSD is used to document the bias and precision of a method in a given sample
matrix.
Refer to Chapter One for definitions of bias and precision, and for the proper data
reduction protocols. MS/MSD samples should be spiked at the same level, and with the same
spiking material, as the corresponding laboratory control sample that is at the project-specific
action level or, when lacking project-specific action levels, at approximately mid-point of the
linear dynamic range. Acceptance criteria should either be defined in the project-specifc
planning documents or set at a laboratory-derived limit developed through the use of historical
analyses per matrix type analyzed. In the absence of project-specific or historical data
generated criteria, these limits should be set at ± 25% of the spiked value for accuracy and 20
relative percent difference (RPD) for precision. Acceptance limits derived from historical data
should be no wider that ± 25% for accuracy and 20% for precision. Refer to Chapter One for
additional guidance. If the bias and precision indicators are outside the laboratory control limits,
if the percent recovery is less than 75% or greater than 125%, or if the relative percent
difference is greater than 20%, then the interference test discussed in Sec. 9.11 should be
conducted.
9.10.1 The relative percent difference between spiked matrix duplicate or
unspiked duplicate determinations is to be calculated as follows:
RPD '
*D1 & D2*
*D1 % D2*
× 100
2
where:
RPD = relative percent difference.
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D1
D2
= first sample value.
= second sample value (spiked or unspiked duplicate).
9.10.2 The spiked sample or spiked duplicate sample recovery should be within
± 25% of the actual value, or within the documented historical acceptance limits for each
matrix.
9.11 If less than acceptable accuracy and precision data are generated, additional
quality control tests (Secs. 9.11.1 and 9.11.2) are recommended prior to reporting concentration
data for the elements in this method. At a minimum these tests should be performed with each
batch of samples prepared/analyzed with corresponding unacceptable data quality results.
These test will then serve to ensure that neither positive nor negative interferences are affecting
the measurement of any of the elements or distorting the accuracy of the reported values. If
matrix effects are confirmed, the laboratory should consult with the data user when feasible for
possible corrective actions which may include the use of alternative or modified test procedures
so that the analysis is not impacted by the same interference.
9.11.1
Post digestion spike addition
If the MS/MSD recoveries are unacceptable, the same sample from which the
MS/MSD aliquots were prepared should also be spiked with a post digestion spike.
Otherwise another sample from the same preparation should be used as an alternative.
An analyte spike is added to a portion of a prepared sample, or its dilution, and should be
recovered to within 80% to 120% of the known value. The spike addition should produce
a minimum level of 10 times and a maximum of 100 times the lower limit of quantitation. If
this spike fails, then the dilution test (Sec. 9.11.2) should be run on this sample. If both
the MS/MSD and the post digestion spike fail, then matrix effects are confirmed.
9.11.2
Dilution test
If the analyte concentration is sufficiently high (minimally, a factor of 10 above the
lower limit of quantitation after dilution), an analysis of a 1:5 dilution should agree within ±
10% of the original determination. If not, then a chemical or physical interference effect
should be suspected.
9.12 Ultra-trace analysis requires the use of clean chemistry preparation and analysis
techniques. Several suggestions for minimizing analytical blank contamination are provided in
Chapter Three.
10.0 CALIBRATION AND STANDARDIZATION
10.1 Set up the instrument with proper operating parameters established as detailed
below. The instrument should be allowed to become thermally stable before beginning (usually
requiring at least 30 min of operation prior to calibration). For operating conditions, the analyst
should follow the instructions provided by the instrument manufacturer.
10.2 Conduct mass calibration and resolution checks in the mass regions of interest.
The mass calibration and resolution parameters are required criteria which must be met prior to
any samples being analyzed. If the mass calibration differs more than 0.1 amu from the true
value, then the mass calibration must be adjusted to the correct value. The resolution must also
be verified to be less than 0.9 amu full width at 10% peak height.
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10.2.1 Before using this procedure to analyze samples, data should be available
documenting the initial demonstration of performance. The required data should
document the determination of the linear dynamic ranges; a demonstration of the desired
method sensitivity and instrument detection limits; and the determination and verification
of the appropriate correction equations or other routines for correcting spectral
interferences. These data should be generated using the same instrument, operating
conditions, and calibration routine to be used for sample analysis. These data should be
kept on file and be available for review by the data user or auditor.
10.2.2 Sensitivity, instrumental detection limit, precision, linear dynamic range,
and interference corrections need to be established for each individual target analyte on
each particular instrument. All measurements (both target analytes and constituents
which interfere with the target analytes) need to be within the instrument linear range
where the correction equations are valid.
10.2.3
The lower limits of quantitation should be established for all isotope
masses utilized for each type of matrix analyzed and for each preparation method used
and for each instrument. These limits are considered the lowest reliable laboratory
reporting concentrations and should be established from the lower limit of quantitation
check sample and then confirmed using either the lowest calibration point or from a lowlevel calibration check standard.
10.2.3.1
Lower limit of quantitation check sample
The lower limit of quantitation check (LLQC) sample should be analyzed
after establishing the lower laboratory reporting limits and on an as needed basis
to demonstrate the desired detection capability. Ideally, this check sample and the
low-level calibration verification standard will be prepared at the same
concentrations with the only difference being the LLQC sample is carried through
the entire preparation and analytical procedure. Lower limits of quantitation are
verified when all analytes in the LLQC sample are detected within ± 30% of their
true value. This check should be used to both establish and confirm the lowest
quantitation limit.
10.2.3.2 The lower limits of quantitation determination using reagent
water represents a best case situation and does not represent possible matrix
effects of real-world samples. For the application of lower limits of quantitation on
a project-specific basis with established data quality objectives, low-level matrixspecific spike studies may provide data users with a more reliable indication of the
actual method sensitivity and minimum detection capabilities.
10.2.4 Specific recommended isotopes for the analytes noted in Sec. 1.2 are
provided in Table 2. Other isotopes may be substituted if they can provide the needed
sensitivity and are corrected for spectral interference. Because of differences among
various makes and models of mass spectrometers, specific instrument operating
conditions cannot be provided. The instrument and operating conditions utilized for
determination must be capable of providing data of acceptable quality for the specific
project and data user. The analyst should follow the instructions provided by the
instrument manufacturer unless other conditions provide similar or better performance for
a given task.
10.3 All masses which could affect data quality should be monitored to determine
potential effects from matrix components on the analyte peaks. The recommended isotopes to
be monitored are listed in Table 2.
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10.4 All analyses require that a calibration curve be prepared to cover the appropriate
concentration range based on the intended application and prior to establishing the linear
dynamic range. Usually, this means the preparation of a calibration blank and mixed calibration
standard solutions (Sec. 7.5), the highest of which would not exceed the anticipated linear
dynamic range of the instrument. Check the instrument standardization by analyzing
appropriate QC samples as follows.
10.4.1 Individual or mixed calibration standards should be prepared from known
primary stock standards every six months to one year as needed based on the
concentration stability as confirmed from the ICV analyses. The analysis of the ICV, which
is prepared from a source independent of the calibration standards, is necessary to verify
the instrument performance once the system has been calibrated for the desired target
analytes. It is recommended that the ICV solution be obtained commercially as a certified
traceable reference material such that an expiration date can be assigned. Alternately,
the ICV solution can be prepared from an independent source on an as needed basis
depending on the ability to meet the calibration verification criteria. If the ICV analysis is
outside of the acceptance criteria, at a minimum the calibration standards must be
prepared fresh and the instrument recalibrated prior to beginning sample analyses.
Consideration should also be given to preparing fresh ICV standards if the new calibration
cannot be verified using the existing ICV standard.
NOTE:
This method describes the use of both a low-level and mid-level ICV standard
analysis. For purposes of verifying the initial calibration, only the mid-level ICV
needs to be prepared from a source other than the calibration standards.
10.4.1.1 The calibration standards should be prepared using the same
type of acid or combination of acids and at similar concentrations as will result in
the samples following processing.
10.4.1.2 The response of the calibration blank should be less than the
response of the typical laboratory lower limit of quantitation for each desired target
analyte. Additionally, if the calibration blank response or continuing calibration
blank verification is used to calculate a theoretical concentration, this value should
be less than the level of acceptable blank contamination as specified in the
approved quality assurance project planning documents. If this is not the case, the
reason for the out-of-control condition must be found and corrected, and the
sample analyses may not proceed or the previous ten samples need to be
reanalyzed.
10.4.2 For the initial and daily instrument operation, calibrate the system
according to the instrument manufacturer’s guidelines using the mixed calibration
standards as noted in Sec. 7.5. The calibration curve should be prepared daily with a
minimum of a calibration blank and a single standard at the appropriate concentration to
effectively outline the desired quantitation range. Flush the system with the rinse blank
(Sec. 7.6.3) between each standard solution. Use the average of at least three
integrations for both calibration and sample analyses. The resulting curve should then be
verified with mid-level and low-level initial calibration verification standards as outlined in
Sec. 10.4.3.
Alternatively, the calibration curve can be prepared daily with a minimum of a
calibration blank and three non-zero standards that effectively bracket the desired sample
concentration range. If low-level as compared to mid- or high-level sample concentrations
are expected, the calibration standards should be prepared at the appropriate
concentrations in order to demonstrate the instrument linearity within the anticipated
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sample concentration range. For all multi-point calibration scenarios, the lowest non-zero
standard concentration should be considered the lower limit of quantitation.
NOTE:
Regardless of whether the instrument is calibrated using only a minimum number
of standards or with a multi-point curve, the upper limit of the quantitation range
may exceed the highest concentration calibration point and can be defined as the
"linear dynamic" range, while the lower limit can be identified as the "lower limit of
quantitation limit" (LLQL) and will be either the concentration of the lowest
calibration standard (for multi-point curves) or the concentration of the low level
ICV/CCV check standard. Results reported outside these limits would not be
recommended unless they are qualified as estimated. See Sec. 10.4.4 for
recommendations on how to determine the linear dynamic range, while the
guidance in this section and Sec. 10.4.3 provide options for defining the lower
limit of quantitation.
10.4.2.1 To be considered acceptable, the calibration curve should
have a correlation coefficient greater than or equal to 0.998. When using a multipoint calibration curve approach, every effort should be made to attain an
acceptable correlation coefficient based on a linear response for each desired
target analyte. If the recommended linear response cannot be attained using a
minimum of three non-zero calibration standards, consideration should be given to
adding more standards, particularly at the lower concentrations, in order to better
define the linear range and the lower limit of quantitation. Conversely, the extreme
upper and lower calibration points may be removed from the multi-point curve as
long as three non-zero points remain such that the linear range is narrowed and
the non-linear upper and/or lower portions are removed. As with the single point
calibration option, the multi-point calibration should be verified with both a mid- and
low-level ICV standard analysis using the same 90 - 110% and 70 - 130%
acceptance criteria, respectively.
10.4.2.2 Many instrument software packages allow multi-point
calibration curves to be "forced" through zero. It is acceptable to use this feature,
provided that the resulting calibration meets the acceptance criteria, and can be
verified by acceptable QC results. Forcing a regression through zero should NOT
be used as a rationale for reporting results below the calibration range defined by
the lowest standard in the calibration curve.
10.4.3 After initial calibration, the calibration curve should be verified by use of
an initial calibration verification (ICV) standard analysis. At a minimum, the ICV standard
should be prepared from an independent (second source) material at or near the midrange of the calibration curve. The acceptance criteria for this mid-range ICV standard
should be ±10% of its true value. Additionally, a low-level initial calibration verification
(LLICV) standard should be prepared, using the same source as the calibration standards,
at a concentration expected to be the lower limit of quantitation. The suggested
acceptance criteria for the LLICV is ±30% of its true value. Quantitative sample analyses
should not proceed for those analytes that fail the second source standard initial
calibration verification, with the exception that analyses may continue for those analytes
that fail the criteria with an understanding these results should be qualified and would be
considered estimated values. Once the calibration acceptance criteria is met, either the
lowest calibration standard or the LLICV concentration can be used to demonstrate the
lower limit of quantitation and sample results should not be quantitated below this lowest
standard. In some cases depending on the stated project data quality objectives, it may
be appropriate to report these results as estimated, however, they should be qualified by
noting the results are below the lower limit of quantitation. Therefore, the laboratory’s
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quantitation limit cannot be reported lower than either the LLICV standard used for the
single point calibration option or the low calibration and/or verification standard used
during initial multi-point calibration. If the calibration curve cannot be verified within these
specified limits for the mid-range ICV and LLICV analyses, the cause needs to be
determined and the instrument recalibrated before samples are analyzed. The analysis
data for the initial calibration verification analyses should be kept on file with the sample
analysis data.
10.4.4 Both the single and multi-point calibration curves should be verified at the
end of each analysis batch and after every 10 samples by use of a continuing calibration
verification (CCV) standard and a continuing calibration blank (CCB). The CCV should be
made from the same material as the initial calibration standards at or near the mid-range
concentration. For the curve to be considered valid, the acceptance criteria for the CCV
standard should be ±10% of its true value and the CCB should contain target analytes less
than the established lower limit of quantitation for any desired target analyte. If the
calibration cannot be verified within the specified limits, the sample analysis must be
discontinued, the cause determined and the instrument recalibrated. All samples following
the last acceptable CCV/CCB must be reanalyzed. The analysis data for the CCV/CCB
should be kept on file with the sample analysis data.
The low level continuing calibration verification (LLCCV) standard should also be
analyzed at the end of each analysis batch. A more frequent LLCCV analysis, i.e., every
10 samples may be necessary if low-level sample concentrations are anticipated and the
system stability at low end of the calibration is questionable. In addition, the analysis of a
LLCCV on a more frequent basis will minimize the number of samples for re-analysis
should the LLCCV fail if only run at the end of the analysis batch. The LLCCV standard
should be made from the same source as the initial calibration standards at the
established lower limit of quantitation as reported by the laboratory. The acceptance
criteria for the LLCCV standard should be ± 30% of its true value. If the calibration cannot
be verified within these specified limits, the analysis of samples containing the affected
analytes at similar concentrations cannot continue until the cause is determined and the
LLCCV standard successfully analyzed. The instrument may need to be recalibrated or
the lower limit of quantitation adjusted to a concentration that will ensure a compliant
LLCCV analysis. The analysis data for the LLCCV standard should be kept on file with the
sample analysis data.
10.5 Verify the magnitude of elemental and molecular-ion isobaric interferences and the
adequacy of any corrections at the beginning of an analytical run or once every 12 hr, whichever
is more frequent. Do this by analyzing the interference check solutions A and AB. The analyst
should be aware that precipitation from solution AB may occur with some elements, specifically
silver. Refer to Sec. 4.0 for a discussion on interferences and potential solutions to those
interferences if additional guidance is needed.
NOTE:
Analysts have noted improved performance in calibration stability if the instrument is
exposed to the interference check solution after cleaning sampler and skimmer cones.
Improved performance is also realized if the instrument is allowed to rinse for 5 or 10
min before the calibration blank is run.
10.6 The linear dynamic range is established when the system is first setup, or
whenever significant instrument components have been replaced or repaired, and on an as
needed basis only after the system has been successfully calibrated using either the single or
multi-point standard calibration approach.
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The upper limit of the linear dynamic range needs to be established for each wavelength
utilized by determining the signal responses from a minimum of three, preferably five, different
concentration standards across the range. The ranges which may be used for the analysis of
samples should be judged by the analyst from the resulting data. The data, calculations and
rationale for the choice of range made should be documented and kept on file. A standard at
the upper limit should be prepared, analyzed and quantitated against the normal calibration
curve. The calculated value should be within 10% (±10%) of the true value. New upper range
limits should be determined whenever there is a significant change in instrument response. At a
minimum, the range should be checked every six months. The analyst should be aware that if
an analyte that is present above its upper range limit is used to apply a spectral correction, the
correction may not be valid and those analytes where the spectral correction has been applied
may be inaccurately reported.
NOTE:
Some metals may exhibit non-linear response curves due to ionization and selfabsorption effects. These curves may be used if the instrument allows it; however the
effective range must be checked and the second order curve fit should have a
correlation coefficient of 0.998 or better. Third order fits are not acceptable. These
non-linear response curves should be revalidated and/or recalculated on a daily basis
using the same calibration verification QC checks as a linear calibration curve. Since
these curves are much more sensitive to changes in operating conditions than the
linear lines, they should be checked whenever there have been moderate equipment
changes. Under these calibration conditions, quantitation is not acceptable above or
below the calibration standards. Additionally, a non-linear curve should be further
verified by calculating the actual recovery of each calibration standard used in the
curve. The acceptance criteria for the calibration standard recovery should be ±10%
of its true value for all standards except the lowest concentration. A recovery of ±30%
of its true value should be achieved for the lowest concentration standard.
10.7 The analyst should (1) verify that the instrument configuration and operating
conditions satisfy the project-specific analytical requirements and (2) maintain quality control
data that demonstrate and confirm the instrument performance for the reported analytical
results.
11.0 PROCEDURE
11.1 Preliminary treatment of most matrices is necessary because of the complexity and
variability of sample matrices. Groundwater and other aqueous samples designated for a
dissolved metals determination which have been prefiltered and acidified will not need acid
digestion. However, all associated QC samples (i.e., method blank, LCS and MS/MSD) must
undergo the same filtration and acidification procedures. Samples which are not digested must
be matrix-matched with the standards. Solubilization and digestion procedures are presented in
Chapter Three, "Inorganic Analytes."
CAUTION: If mercury is to be analyzed, the digestion procedure must use mixed nitric and
hydrochloric acids through all steps of the digestion. Mercury will be lost if the
sample is digested when hydrochloric acid is not present. If it has not already
been added to the sample as a preservative, Au should be added to give a final
concentration of 2 mg/L (use 2.0 mL of 7.4.12 per 100 mL of sample) to preserve
the mercury and to prevent it from plating out in the sample introduction system.
11.2 Initiate appropriate operating configuration of the instrument’s computer according
to the instrument manufacturer's instructions.
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11.3 Set up the instrument with the proper operating parameters according to the
instrument manufacturer's instructions.
11.4 Operating conditions -- The analyst should follow the instructions provided by the
instrument manufacturer. Allow at least 30 min for the instrument to equilibrate before analyzing
any samples. This must be verified by an analysis of the tuning solution (Sec. 7.10) at least four
integrations with relative standard deviations of #5% for the analytes contained in the tuning
solution.
CAUTION: The instrument should have features that protect itself from high ion currents. If
not, precautions must be taken to protect the detector from high ion currents. A
channel electron multiplier or active film multiplier suffers from fatigue after being
exposed to high ion currents. This fatigue can last from several seconds to hours
depending on the extent of exposure. During this time period, response factors are
constantly changing, which invalidates the calibration curve, causes instability, and
invalidates sample analyses.
11.5
Calibrate the instrument following the procedure outlined in Sec. 10.0.
11.6
Flush the system with the rinse blank solution (Sec. 7.6.3) until the signal levels
return to the DQO or method's levels of quantitation (usually about 30 sec) before the analysis
of each sample (see Sec. 10.0). Nebulize each sample until a steady-state signal is achieved
(usually about 30 sec) prior to collecting data. Flow-injection systems may be used as long as
they can meet the performance criteria of this method.
11.7 Regardless of whether the initial calibration is performed using a single high
standard and the calibration blank or the multi-point option, the laboratory should analyze an
LLCCV (Sec. 10.4.4). For all analytes and determinations, the laboratory must analyze an ICV
and LLICV (Sec. 10.4.3) immediately following daily calibration. It is recommended that a CCV
LLCCV, and CCB (Sec. 10.4.4) be analyzed after every ten samples and at the end of the
analysis batch.
11.8 Dilute and reanalyze samples that are more concentrated than the linear range for
an analyte (or species needed for a correction) or measure an alternate but less-abundant
isotope. The linearity at the alternate mass must be confirmed by appropriate calibration (see
Sec. 10.2 and 10.4). Alternatively apply solid phase chelation chromatography to eliminate the
matrix as described in Sec. 4.4.
12.0 DATA ANALYSIS AND CALCULATIONS
12.1 The quantitative values must be reported in appropriate units, such as micrograms
per liter (µg/L) for aqueous samples and milligrams per kilogram (mg/kg) for solid samples. If
dilutions were performed, the appropriate corrections must be applied to the sample values. All
results should be reported with up to three significant figures.
12.2 If appropriate, or required, calculate results for solids on a dry-weight
basis as follows:
(1) A separate determination of percent solids must be performed.
(2) The concentrations determined in the digest are to be reported on
the basis of the dry weight of the sample.
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Concentration (dry weight)(mg/kg) '
C x V
W x S
Where,
C = Digest Concentration (mg/L)
V = Final volume in liters after sample preparation
W = Weight in kg of wet sample
S=
% Solids
100
Calculations must include appropriate interference corrections (see Sec. 4.2 for
examples), internal-standard normalization, and the summation of signals at 206, 207, and 208
m/z for lead (to compensate for any differences in the abundances of these isotopes between
samples and standards).
12.3 Results must be reported in units commensurate with their intended use and all
dilutions must be taken into account when computing final results.
13.0 METHOD PERFORMANCE
13.1 Performance data and related information are provided in SW-846 methods only as
examples and guidance. The data do not represent required performance criteria for users of
the methods. Instead, performance criteria should be developed on a project-specific basis,
and the laboratory should establish in-house QC performance criteria for the application of this
method. These performance data are not intended to be and must not be used as absolute QC
acceptance criteria for purposes of laboratory accreditation.
13.2 In an EPA multi-laboratory study (Ref. 12), twelve laboratories applied the ICP-MS
technique to both aqueous and solid samples. Table 3 summarizes the method performance
data for aqueous samples. Performance data for solid samples are provided in Table 4. These
data are provided for guidance purposes only.
13.3 Table 5 summarizes the method performance data for aqueous and sea water
samples with interfering elements removed and samples preconcentrated prior to analysis.
Table 6 summarizes the performance data for a simulated drinking water standard. These data
are provided for guidance purposes only.
14.0 POLLUTION PREVENTION
14.1 Pollution prevention encompasses any technique that reduces or eliminates the
quantity and/or toxicity of waste at the point of generation. Numerous opportunities for pollution
prevention exist in laboratory operation. The EPA has established a preferred hierarchy of
environmental management techniques that places pollution prevention as the management
option of first choice. Whenever feasible, laboratory personnel should use pollution prevention
techniques to address their waste generation. When wastes cannot be feasibly reduced at the
source, the Agency recommends recycling as the next best option.
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14.2 For information about pollution prevention that may be applicable to laboratories
and research institutions consult Less is Better: Laboratory Chemical management for Waste
Reduction available from the American Chemical Society’s Department of Government
Relations and Science Policy, 1155 16th St., N.W. Washington, D.C. 20036, http://www.acs.org.
15.0 WASTE MANAGEMENT
The Environmental Protection Agency requires that laboratory waste management
practices be conducted consistent with all applicable rules and regulations. The Agency urges
laboratories to protect the air, water, and land by minimizing and controlling all releases from
hoods and bench operations, complying with the letter and spirit of any sewer discharge permits
and regulations, and by complying with all solid and hazardous waste regulations, particularly
the hazardous waste identification rules and land disposal restrictions. For further information
on waste management, consult The Waste Management Manual for Laboratory Personnel
available from the American Chemical Society at the address listed in Sec. 14.2.
16.0 REFERENCES
1. G. Horlick, et al., Spectrochim. Acta 40B, 1555 (1985).
2. A. L. Gray, Spectrochim. Acta 40B, 1525 (1985); 41B, 151 (1986).
3. S. H. Tan and G. Horlick, Appl. Spectrosc. 40, 445 (1986).
4. M. A. Vaughan and G. Horlick, Appl. Spectrosc. 40, 434 (1986).
5. N. E. Holden, "Table of the Isotopes," in D. R. Lide, Ed., CRC Handbook of Chemistry and
Physics, 74th Ed., CRC Press, Boca Raton, FL, 1993.
6. T. A. Hinners, E. Heithmar, E. Rissmann, and D. Smith, Winter Conference on Plasma
Spectrochemistry, Abstract THP18; p. 237, San Diego, CA (1994).
7. F. E. Lichte, et al., Anal. Chem. 59, 1150 (1987).
8. E. H. Evans and L. Ebdon, J. Anal. At. Spectrom. 4, 299 (1989).
9. D. Beauchemin, et al., Spectrochim. Acta 42B, 467 (1987).
10. R. S. Houk, Anal. Chem. 58, 97A (1986).
11. J. J. Thompson and R. S. Houk, Appl. Spectrosc. 41, 801 (1987).
12. W. R. Newberry, L. C. Butler, M. L. Hurd, G. A. Laing, M. A. Stapanian, K. A. Aleckson,
K.A., D. E. Dobb, J. T. Rowan, J.T., and F. C. Garner, "Final Report of the Multi-Laboratory
Evaluation of Method 6020 CLP-M Inductively Coupled Plasma-Mass Spectrometry" (1989).
13. Daniel B. Taylor, H. M. Kingston, D. J. Nogay, D. Koller, and R. Hutton, "On-Line Solidphase Chelation for the Determination of Eight Metals in Environmental Waters by
Inductively Coupled Plasma Mass Spectrometry."
14. H. M. Kingston, A. Siriraks, and J. M. Riviello, Patent Number 5,126,272, "A Method and
Apparatus for Detecting Transition and Rare Earth Elements in a Matrix," U.S. Patent, Filed
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U.S. Patent Office, March 1989, 31 pages, Granted June 30, 1992, Patent held by US
Government.
15. H. M. Kingston, A. Siriraks, and J. M. Riviello, Patent Number 5,244,634 , "A Method and
Apparatus for Detecting Transition and Rare Earth Elements in a Matrix," U.S. Patent, Filed
U.S. Patent Office, March 1989, 31 pages, Granted Sept. 14, 1993, Patent held by US
Government.
16. D. E. Dobb, J. T. Rowan, and D. Cardenas, Lockheed Environmental Systems and
Technologies Co., Las Vegas, NV; and L. C. Butler, and E. M. Heithmar, E.M., U.S.EPA,
Las Vegas, NV; "Determination of Mercury by ICP-MS."
17.0
TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA
The following pages contain the tables referenced by this method. A flow diagram of the
procedure follows the tables.
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TABLE 1
RECOMMENDED INTERFERENCE CHECK SAMPLE COMPONENTS
AND CONCENTRATIONS
Solution
Solution A
Solution AB
Component
Concentration (mg/L)
Concentration (mg/L)
Al
100.0
100.0
Ca
300.0
300.0
Fe
250.0
250.0
Mg
100.0
100.0
Na
250.0
250.0
P
100.0
100.0
K
100.0
100.0
S
100.0
100.0
C
200.0
200.0
Cl
2000.0
2000.0
Mo
2.0
2.0
Ti
2.0
2.0
As
0.0
0.100
Cd
0.0
0.100
Cr
0.0
0.200
Co
0.0
0.200
Cu
0.0
0.200
Mn
0.0
0.200
Hg
0.0
0.020
Ni
0.0
0.200
Se
0.0
0.100
Ag
0.0
0.050
V
0.0
0.200
0.100
Zn
0.0
These data are provided for guidance purposes only.
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TABLE 2
RECOMMENDED ISOTOPES FOR SELECTED ELEMENTS
Element of Interest
Aluminum
Antimony
Arsenic
Barium
Beryllium
Bismuth (IS)
Cadmium
Calcium (I)
Chlorine (I)
Chromium
Cobalt
Copper
Germanium (IS)
Holmium (IS)
Indium (IS)
Iron (I)
Lanthanum (I)
Lead
Lithium (IS)
Magnesium (I)
Manganese
Mercury
Molybdenum (I)
Nickel
Potassium (I)
Rhodium (IS)
Scandium (IS)
Selenium
Silver
Sodium (I)
Terbium (IS)
Thallium
Vanadium
Tin (I)
Yttrium (IS)
Zinc
Mass(es)
27
121, 123
75
138, 137, 136, 135, 134
9
209
114, 112, 111, 110, 113, 116, 106
42, 43, 44, 46, 48
a
35, 37, (77, 82)
52, 53, 50, 54
59
63, 65
74
165
115, 113
56, 54, 57, 58
139
208, 207, 206, 204
b
6 ,7
24, 25, 26
55
202, 200, 199, 201
a
98, 96, 92, 97, 94, (108)
58, 60, 62, 61, 64
39
103
45
80, 78, 82, 76, 77, 74
107, 109
23
159
205, 203
51, 50
120, 118
89
64, 66, 68, 67, 70
a
These masses are also useful for interference correction (Sec. 4.2).
Internal standard must be enriched in the 6Li isotope. This minimizes interference from
indigenous lithium.
NOTE: Method 6020 is recommended for only those analytes listed in Sec.1.2. Other elements are
included in this table because they are potential interferents (labeled I) in the determination of
recommended analytes, or because they are commonly used internal standards (labeled IS). Isotopes
are listed in descending order of natural abundance. The most generally useful isotopes are underlined
and in boldface, although certain matrices may require the use of alternative isotopes.
b
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TABLE 3
EXAMPLE ICP-MS MULTI-LABORATORY PRECISION AND ACCURACY DATA
FOR AQUEOUS SOLUTIONS
a
Element
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Comparability
Range
95 - 100
d
97 - 114
91 - 99
103 - 107
98 - 102
99 - 107
95 - 105
101 - 104
85 - 101
91 - 900
71 - 137
98 - 102
95 - 101
98 - 101
101 - 114
102 - 107
104 - 105
82 - 104
88 - 97
107 - 142
93 - 102
b
c
%RSD Range
N
S
11 - 14
5.0 - 7.6
7.1 - 48
4.3 - 9.0
8.6 - 14
4.6 - 7.2
5.7 - 23
13 - 27
8.2 - 8.5
6.1 - 27
11 - 150
11 - 23
10 - 15
8.8 - 15
6.1 - 6.7
9.9 - 19
15 - 25
5.2 - 7.7
24 - 43
9.7 - 12
23 - 68
6.8 - 17
14 - 14
16 - 16
16 - 16
16 - 16
13 - 14
18 - 20
17 - 18
16 - 18
18 - 18
17 - 18
10 - 12
17 - 18
16 - 16
18 - 18
18 - 18
11 - 12
12 - 12
13 - 16
9 - 10
18 - 18
8 - 13
16 - 18
4
3
4
5
3
3
5
4
3
5
5
6
5
4
2
5
3
2
5
3
3
5
Data obtained from Ref. 12.
Comparability refers to the percent agreement of mean ICP-MS values to those of the
reference technique (ICP-AES or GFAA).
b
N is the range of the number of ICP-MS measurements where the analyte values exceed the
limit of quantitation (3.3 times the average IDL value). A larger number gives a more reliable
comparison.
c
S is the number of samples with results greater than the limit of quantitation.
d
No comparability values are provided for antimony because of evidence that the reference
data is affected by an interference.
a
These data are provided for guidance purposes only.
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TABLE 4
EXAMPLE ICP-MS MULTI-LABORATORY PRECISION AND ACCURACY DATA
FOR SOLID MATRICES
a
Comparability
b
c
%RSD Range
N
S
Range
Aluminum
83 - 101
11 - 39
13 - 14
7
Antimony
d
12 - 21
15 - 16
2
Arsenic
79 - 102
12 - 23
16 - 16
7
Barium
100 - 102
19 - 34
15 - 16
7
Beryllium
50 - 87
8.6 - 14
12 - 14
5
Cadmium
93 - 100
6.2 - 25
19 - 20
5
Calcium
95 - 109
4.1 - 27
15 - 17
7
Chromium
77 - 98
11 - 32
17 - 18
7
Cobalt
43 - 102
15 - 30
17 - 18
6
Copper
90 - 109
9.0 - 25
18 - 18
7
Iron
87 - 99
6.7 - 21
12 - 12
7
Lead
90 - 104
5.9 - 28
15 - 18
7
Magnesium
89 - 111
7.6 - 37
15 - 16
7
Manganese
80 - 108
11 - 40
16 - 18
7
Nickel
87 - 117
9.2 - 29
16 - 18
7
Potassium
97 - 137
11 - 62
10 - 12
5
Selenium
81
39
12
1
Silver
43 - 112
12 - 33
15 - 15
3
Sodium
100 - 146
14 - 77
8 - 10
5
Thallium
91
33
18
1
Vanadium
83 - 147
20 - 70
6 - 14
7
Zinc
84 - 124
14 - 42
18 - 18
7
Data obtained from Ref. 12.
a
Comparability refers to the percent agreement of mean ICP-MS values to those of the
reference technique.
b
N is the range of the number of ICP-MS measurements where the analyte values exceed the
limit of quantitation (3.3 times the average IDL value).
c
S is the number of samples with results greater than the limit of quantitation.
d
No comparability values are provided for antimony because of evidence that the reference
data is affected by an interference.
Element
These data are provided for guidance purposes only.
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TABLE 5
EXAMPLE METHOD PERFORMANCE DATA FOR AQUEOUS AND SEA WATER SAMPLESA
WITH INTERFERING ELEMENTS REMOVED
AND SAMPLES PRECONCENTRATED PRIOR TO ANALYSIS
CONCENTRATION (ng/mL)B
ELEMENT
Manganese
Nickel
Cobalt
Copper
Zinc
Copper
Zinc
Cadmium
Cadmium
Lead
Lead
Lead
ISOTOPE
55
58
59
63
64
65
66
112
114
206
207
208
9.0 mL
1.8±0.05
0.32±0.018
0.033±0.002
0.68±0.03
1.6±0.05
0.67±0.03
1.6±0.06
0.020±0.0015
0.020±0.0009
0.013±0.0009
0.014±0.0005
0.014±0.0006
27.0 mL
1.9±0.2
0.32±0.04
0.028±0.003
0.63±0.03
1.8±0.15
0.6±0.05
1.8±0.2
0.019±0.0018
0.019±0.002
0.019±0.0011
0.019±0.004
0.019±0.002
CERTFIED
1.99±0.15
0.30±0.04
0.025±0.006
0.68±0.04
1.97±0.12
0.68±0.04
1.97±0.12
0.019±0.004
0.019±0.004
0.019±0.006
0.019±0.006
0.019±0.006
Data obtained from Ref. 12.
The dilution of the sea-water during the adjustment of pH produced 10 mL samples containing 9 mL of sea-water and 30
mL samples containing 27 mL of sea-water. Samples containing 9.0 mL of CASS-2, n=5; samples containing 27.0 mL of
CASS-2, n=3.
B
Concentration (ng/mL) ± 95% confidence limits.
A
These data are provided for guidance purposes only.
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TABLE 6
ANALYSIS OF NIST SRM 1643b, TRACE METALS IN WATERA
AND SAMPLES PRECONCENTRATED PRIOR TO ANALYSIS
CONCENTRATION (ng/mL)B
ELEMENT
ISOTOPE
Manganese
55
Nickel
58
Cobalt
59
Nickel
60
Copper
63
Zinc
64
Copper
65
Zinc
66
Cadmium
111
Cadmium
112
Cadmium
114
Lead
206
Lead
207
Lead
208
Data obtained from Ref. 12.
A
B
DETERMINED
30±1.3
50±2
27±1.3
51±2
23±1.0
67±1.4
22±0.9
67±1.8
20±0.5
19.9±0.3
19.8±0.4
23±0.5
23.9±0.4
24.2±0.4
CERTFIED
28±2
49±3
26±1
49±3
21.9±0.4
66±2
21.9±0.4
66±2
20±1
20±1
20±1
23.7±0.7
23.7±0.7
23.7±0.7
5.0 mL samples, n=5.
Concentration (ng/mL) ± 95% confidence limits.
These data are provided for guidance purposes only.
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TABLE 7
COMPARISON OF TOTAL MERCURY RESULTS IN HEAVILY CONTAMINATED SOILS
Mercury in µg/g
Soil Sample
ICP-MS
CVAA
1
27.8
29.2
2
442
376
3
64.7
58.2
4
339
589
5
281
454
6
23.8
21.4
7
217
183
8
157
129
9
1670
1360
10
73.5
64.8
11
2090
1830
12
96.4
85.8
13
1080
1190
14
294
258
15
3300
2850
16
301
281
17
2130
2020
18
247
226
19
2630
Source: Ref. 16.
These data are provided for guidance purposes only.
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METHOD 6020
INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
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