Metals, Atomic Emission Spectrometry, Inductively Coupled Plasma (ICP)
Metals, Atomic Emission Spectrometry, Inductively Coupled Plasma (ICP)
Metals, Atomic Emission Spectrometry, Inductively Coupled Plasma (ICP)
plasma (ICP)
Parameters and Codes:
Metals, dissolved,I-1472-87 (see below)
Parameter Code Parameter Code
Barium (µg/L as Ba) 01005 Magnesium (mg/L as Mg) 00925
Beryllium (µg/L as Be) 01010 Manganese (µg/L as Mn) 01056
Cadmium (µg/L as Cd) 01025 Molybdenum (µg/L as Mo) 01060
Calcium (mg/L as Ca) 00915 Nickel (µg/L as Ni) 01065
Chromium (µg/L as Cr) 01030 Silica (mg/L as Si02) 00955
Cobalt (µg/L as Co) 01035 Silver (µg/L as Ag) 01075
Copper (µg/L as Cu) 01040 Sodium (mg/L as Na) 00930
Iron (µg/L as Fe) 01046 Strontium (µg/L as Sr) 01080
Lead (µg/L as Pb) 01049 Vanadium (µg/L as V) 01085
Lithium (µg/L as Li) 01130 Zinc (µg/L as Zn) 01090
1. Application
1.1 This method is used only for the determination of dissolved metals in
water samples that have a measured specific conductance of less than 2,000 µS/cm
at 25°C. The concentration limits are listed in table 8. Samples containing analyte
concentrations greater than the maximum concentration limit can be analyzed for
calcium, magnesium, silica, and sodium if the sample is diluted and if, after
dilution, the specific conductance is less than 2,000 µS/cm. Trace metals also can
be determined after appropriate dilution in samples that have a measured specific
conductance greater than 2,000 µS/cm; however, detection levels and sensitivity
will change proportionally. This modified method was implemented in the
National Water Quality Laboratory In August 1987.
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Table 8.--Concentration limits of metals for inductively coupled plasma
[µg/L, microgram per liter; mg/L, milligram per liter]
1.3 The inductively coupled plasma (ICP) methods approved for U.S.
Geological Survey use are linked to a specific instrument and associated software.
This does not imply endorsement of one product over another.
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2. Summary of method
All metals are determined simultaneously on a single sample by a direct-reading
emission spectrometric method using an inductively coupled argon plasma as an
excitation source. Samples are pumped into a crossflow pneumatic nebulizer, and
introduced into the plasma through a spray chamber and torch assembly. Each analysis is
determined on the basis of the average of three replicate integrations, each of which is
background corrected by a spectrumshifting technique except for lithium (670.7 nm) and
sodium (589.0 nm). A series of five mixed-element standards and a blank are used for
calibration.
3. Interferences
4. Apparatus
4.1.1 Autosampler.
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NOTE 1. Operating conditions are approximate and will vary from instrument to
instrument.
Incident radio frequency power 1.25 kW
Reflected radio frequency power <10 W
Vertical observation position 16 mm above load coil
Horizontal observation position Center
Argon head pressure 40 lb/in2
Sample argon pressure for crossflow 17 lb/in2
nebulizer
Sample argon flow rate for crossflow 0.9 L/min
nebulizer
Coolant argon flow rate 18 L/min
Sample pumping rate for 10 percent above aspiration
crossflow nebulizer
Refractor plate position Optimized for Hg profile
Spectrum shifter 0.03 nm on high side of
wavelength
5. Reagents
5.1.1 Aqua regia: Cautiously mix three parts concentrated HCl (sp gr
1.19) and one part concentrated HNO3 (sp gr 1.41) just before use.
5.1.2 Hydrochloric acid, 6M: Add 500 mL concentrated HCl (sp gr 1.19) to 400
mL water, and dilute to 1 L.
5.2 Water: All references to water shall be understood to mean ASTM Type I
reagent water (American Society for Testing and Materials, 1991).
5.3 Prepare standard stock solutions from Spex HiPure grade chemicals or
equivalent. Dry all salts for 1 h at 105°C unless otherwise specified. Do not dry hydrated
salts. Clean all metals thoroughly with the appropriate acid, and dry prior to weighing.
5.3.1 Barium standard solution 1, 1.00 mL = 1,000 µg Ba: Dissolve 1.512 g
BaCl2 dried at 180°C for 1 h and cooled in a desiccator, in a 1 ,000-mL volumetric flask
containing 100 mL water. In a well-ventilated hood, slowly add 100 mL concentrated
HNO3 (sp gr 1.41) while stirring. After the BaCl2 has dissolved, dilute to 1 ,000 mL with
water.
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5.3.2 Beryllium standard solution 1, 1.00 mL = 1,000 µg Be: Transfer 1.000 g
Be flakes into a 1 ,000-mL volumetric flask with minimum water. Use a well-ventilated
hood (Caution, see Note 2). Add 90 mL concentrated HNO3 (sp gr 1.41) and 10 mL
concentrated HCl (sp gr 1.19). Heat to increase rate of dissolution. Cool and dilute to
1,000 mL with water.
5.3.4 Calcium (1) standard solution 1, 1.00 mL = 1,000 µg Ca: Weigh 2.497 3 g
CaCO3 dried at 180°C for 1 h and quickly transfer into a 1 ,000-mL volumetric flask
containing 100 mL water. Dissolve cautiously with 10 mL concentrated HNO3 (sp gr
1.41). Cool and dilute the solution to 1,000 mL with water.
5.3.5 Calcium (2) standard solution I, 1.00 mL = 5,000 µg Ca: Dry 12.4865 g
CaCO3 at 180°C for 1 h and cool in a desiccator. Weigh quickly, transfer into a 1,000-mL
volumetric flask containing 100 mL water, and dissolve cautiously with 10 mL
concentrated HNO3 (sp gr 1.41). Dilute to 1,000 mL with water. After cooling, adjust
volume to 1,000 mL.
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5.3.9 Iron standard solution 1, 1.00 mL = 1,000 µg Fe: Transfer 1.000 g Fe
powder into a 1,000-mL volumetric flask with minimum water. Place flask in hood and,
while stirring, add 15 mL concentrated HCI (sp gr 1.19). Heat to increase rate of
dissolution. After dissolution, slowly add 85 mL concentrated HNO3 (sp gr 1.41). Cool
and dilute to 1,000 mL with water.
5.3.11 Lithium standard solution I, 1.00 mL = 1,000 µg Li: Dry LiCO3 in oven at
180°C for 2 h, cool, and transfer 5.3235 g into a 1,000-mL volumetric flask containing
100 mL water. Slowly add 10 mL concentrated HNO3 (sp gr 1.41). Dilute to 1,000 mL
with water. .
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5.3.15 Nickel standard solution I, 1.00 mL = 1,000 µg Ni: Transfer 1.000 g Ni
powder into a 1,000-mL volumetric flask containing 100 mL water. In a well-ventilated
hood while stirring, slowly add 100 mL concentrated HNO3 (sp gr 1.41). Heat and stir for
30 minutes or until dissolution is complete. Cool and dilute to 1,000 mL with water.
5.4 Standard solution II, 1.00 mL = 100 µg metal [except calcium (2) and
sodium, 1.00 mL = 500 µg]: Dilute 100 mL of each individual metal standard solution I
to 1,000 mL with water.
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5.5Mixed working standard solutions
5.5.1 Prepare five mixed working standard solutions as follows: Pipet 25.0 mL of
each appropriate standard solution II into a 250-mL volumetric flask. Dilute to 250 mL
with water. Transfer to acid-rinsed PTFE bottle for storage. Fresh mixed standards need
to be prepared weekly. Final concentration will be 1.00 mL = 10.0 µg for all metals with
the exception of sodium and calcium (2), which will be 1.00 mL = 50.0 µg. Composition
for mixed standard solutions will be as follows:
5.5.2 Mixed standard solution I--Iron, cadmium, chromium, lead, and zinc.
6. Procedure
6.1 Set up instrument with proper operating conditions (paragraph 4.2) and
ignite plasma. Warm the instrument for 30 minutes prior to standardization.
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6.3 Aspirate a profiling solution or position the mercury pen lamp in front of
the entrance slit. Initiate the profile computer command and profile the instrument by
averaging the micrometer settings obtained at identical intensity positions on each side of
the profiling spectral line. Position the micrometer to the average setting.
6.4 Standardize the data system by running a blank and the series of five mixed
standard solutions. Pump rinse solution for 30 seconds between standards. Allow 30
seconds for equilibration each time a new solution is introduced.
7. Calculations
7.1 All calculations are performed internally by the computer data system. The
compound SiO2 will be labeled Si. Headings are used to identify the results.
7.2 If dilutions were performed, multiply the results by the appropriate dilution
factor using computer software.
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8. Report
8.1 All results are printed out directly in the appropriate reporting units.
.8.2.1 Calcium (00915), magnesium (00925), silica (00955), and sodium (00930):
less than 10 mg/L, one decimal; 10 mg/L and greater, two significant figures.
8.2.2 Beryllium (01010), cadmium (01025), manganese (01056), silver (01075),
and strontium (01080): less than 10 µg/L, nearest microgram per liter; 10 µg/L and
greater, two significant figures.
8.2.3 Barium (01005), chromium (01030), cobalt (01035), iron (01046), lithium
(01130), vanadium (01085), and zinc (01090): less than 10 µg/L, nearest microgram per
liter to the lower limit of detection as specified in table 8; 10 µg/L and greater, two
significant figures.
8.2.4 Copper (01040), lead (01049), molybdenum (01060), and nickel (01065):
less than 100 µg/L, nearest 10 µg/L; 100 µg/L and greater, two significant figures.
9. Precision
Within its designated range, single-operator precision of the method for each metal
can be expressed as listed in table 9. A minimum of 10 replicates was analyzed to obtain
each regression equation shown.
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Table 9.-- Single-operator precision data for inductively coupled plasma
[µg/L, microgram per liter; mg/L, milligram per liter]
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9.3.1 Chromium
Number of replicates Mean Standard Relative standard
(µg/L) deviation deviation (percent)
(µg/L)
11 1.1 1.2 109
12 10.9 .76 7
18 16.6 1.0 6
11 19.7 1.4 7
12 24.6 .98 4
9.3.2 Nickel
Number of replicates Mean Standard Relative standard
(µg/L) deviation (µg/L) deviation (percent)
12 10.6 7.0 66
12 12.7 4.1 32
9 19.8 5.3 27
12 25.2 3.3 13
18 46.8 4.2 9
9.3.3 Silver
Number of replicates Mean Standard Relative standard
(µg/L) deviation deviation (percent)
(µg/L)
9 0.37 0.38 102
12 2.48 .52 21
12 3.87 .66 17
12 4.95 1.5 30
18 10.4 1.8 17
Reference
American Society for Testing and Materials, 1991, Annual book of ASTM standards,
Section 11, Water: Philadelphia, v. 11.01, p. 45-47.
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