PREAMBLE (NOT PART OF THE STANDARD)

END OF PREAMBLE (NOT PART OF THE STANDARD)

STANDARD METHODS: FOR THE
EXAMINATION OF
WATER AND WASTEWATER

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      Standard methods for the examination of water and wastewater.
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3-8

3111 METALS BY FLAME ATOMIC ABSORPTION SPECTROMETRY^*

3111 A. Introduction

1. Principle

Atomic absorption spectrometry resembles emission flame photometry in that a sample is aspirated into a flame and atomized. The major difference is that in flame photometry the amount of light emitted is measured, whereas in atomic absorption spectrometry a light beam is directed through the flame, into a monochromator, and onto a detector that measures the amount of light absorbed by the atomized element in the flame. For some metals, atomic absorption exhibits superior sensitivity over flame emission. Because each metal has its own characteristic absorption wavelength, a source lamp composed of that element is used; this makes the method relatively free from spectral or radiation interferences. The amount of energy at the characteristic wavelength absorbed in the flame is proportional to the concentration of the element in the sample over a limited concentration range. Most atomic absorption instruments also are equipped for operation in an emission mode.

2. Selection of Method

See Section 3110.
^* Approved by Standard Methods Committee. 1989.
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3. Interferences

a. Chemical interference: Many metals can be determined by direct aspiration of sample into an air-acetylene flame. The most troublesome type of interference is termed “chemical” and results from the lack of absorption by atoms bound in molecular combination in the flame. This can occur when the flame is not hot enough to dissociate the molecules or when the dissociated atom is oxidized immediately to a compound that will not dissociate further at the flame temperature. Such interferences may be reduced or eliminated by adding specific elements or compounds to the sample solution. For example, the interference of phosphate in the magnesium determination can be overcome by adding lanthanum. Similarly, introduction of calcium eliminates silica interference in the determination of manganese. However, silicon and metals such as aluminum, barium, beryllium, and vanadium require the higher-temperature, nitrous oxide-acetylene flame to dissociate their molecules. The nitrous oxide-acetylene flame also can be useful in minimizing certain types of chemical interferences encountered in the air-acetylene flame. For example, the interference caused by high concentrations of phosphate in the determination of calcium in the air-acetylene flame does not occur in the nitrous oxide-acetylene flame.
MIBK extractions with APDC (see 3111C) are particularly useful where a salt matrix interferes, for example, in seawater. This procedure also concentrates the sample so that the detection limits are extended.
Brines and seawater can be analyzed by direct aspiration but sample dilution is recommended. Aspiration of solutions containing high concentrations of dissolved solids often results in solids buildup on the burner head. This requires frequent shutdown of the flame and cleaning of the burner head. Preferably use background correction when analyzing waters that contain in excess of 1% solids, especially when the primary resonance line of the element of interest is below 240 nm. Make more frequent recovery checks when analyzing brines and seawaters to insure accurate results in these concentrated and complex matrices.
Barium and other metals ionize in the flame, thereby reducing the ground state (potentially absorbing) population. The addition of an excess of a cation (sodium, potassium, or lithium) having a similar or lower ionization potential will overcome this problem. The wavelength of maximum absorption for arsenic is 193.7 nm and for selenium 196.0 nm—wavelengths at which the air-acetylene flame absorbs intensely. The sensitivity for arsenic and selenium can be improved by conversion to their gaseous hydrides and analyzing them in either a nitrogen-hydrogen or an argon-hydrogen flame with a quartz tube (see Section 3114).
b. Background correction: Molecular absorption and light scattering caused by solid particles in the flame can cause erroneously high absorption values resulting in positive errors. When such phenomena occur, use background correction to obtain accurate values. Use any one of three types of background correction: continuum-source, Zeeman, or Smith-Hieftje correction.
1) Continuum-source background correction—A continuum source background corrector utilizes either a hydrogen-filled hollow cathode lamp with a metal cathode or a deuterium are lamp. When both the line source hollow-cathode lamp and the continuum source are placed in the same optical path and are time-shared, the broadband background from the elemental signal is subtracted electronically, and the resultant signal will be back-ground-compensated.
Both the hydrogen-filled hollow-cathode lamp and deuterium are lamp have lower intensities than either the line source hollow-cathode lamp or electrodeless discharge lamps. To obtain a valid correction, match the intensities of the continuum source with the line source hollow-cathode or electrodeless discharge lamp. The matching may result in lowering the intensity of the line source or increasing the slit width: these measures have the disadvantage of raising the detection limit and possibly causing nonlinearity of the calibration curve. Background correction using a continuum source corrector is susceptible to interference from other absorbing lines in the spectral bandwidth. Miscorrection occurs from significant atomic absorption of the continuum source radiation by elements other than that being determined. When a line source hollow-cathode lamp is used without background correction, the presence of an absorbing line from another element in the spectral bandwidth will not cause an interference unless it overlaps the line of interest.
Continuum-source background correction will not remove direct absorption spectral overlap, where an element other than that being determined is capable of absorbing the line radiation of the element under study.
2) Zeeman background correction—This correction is based on the principle that a magnetic field splits the spectral line into two linearly polarized light beams parallel and perpendicular to the magnetic field. One is called the pi (π) component and the other the sigma (σ) component. These two light beams have exactly the same wavelength and differ only in the plane of polarization. The π line will be absorbed by both the atoms of the element of interest and by the background caused by broadband absorption and light scattering of the sample matrix. The σ line will be absorbed only by the background.
Zeeman background correction provides accurate background correction at much higher absorption levels than is possible with continuum source background correction systems. It also virtually eliminates the possibility of error from structured background. Because no additional light sources are required, the alignment and intensity limitations encountered using continuum sources are eliminated.
Disadvantages of the Zeeman method include reduced sensitivity for some elements, reduced linear range, and a “rollover” effect whereby the absorbance of some elements begins to decrease at high concentrations, resulting in a two-sided calibration curve.
3) Smith-Hieftje background correction—This correction is based on the principle that absorbance measured for a specific element is reduced as the current to the hollow cathode lamp is increased while absorption of nonspecific absorbing substances remains identical at all current levels. When this method is applied, the absorbance at a high-current mode is subtracted from the absorbance at a low-current mode. Under these conditions, any absorbance due to nonspecific background is subtracted out and corrected for.
Smith-Hieftje background correction provides a number of advantages over continuum-source correction. Accurate correction at higher absorbance levels is possible and error from structured background is virtually eliminated. In some cases, spectral interferences also can be eliminated. The usefulness of Smith-Hieftje background correction with electrodeless discharge lamps has not yet been established.
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4. Sensitivity, Detection Limits, and Optimum Concentration Ranges

The sensitivity of flame atomic absorption spectrometry is defined as the metal concentration that produces an absorption of 1% (an absorbance of approximately 0.0044). The instrument detection limit is defined here as the concentration that produces absorption equivalent to twice the magnitude of the background fluctuation. Sensitivity and detection limits vary with the instrument, the element determined, the complexity of the matrix, and the technique selected. The optimum concentration range usually starts from the concentration of several times the sensitivity and extends to the concentration at which the calibration curve starts to flatten. To achieve best results, use concentrations of samples and standards within the optimum concentration range of the spectrometer. See Table 3111:I for indication of concentration ranges measurable with conventional atomization. In many instances the concentration range shown in Table 3111:I may be extended downward either by scale expansion or by integrating the absorption signal over a long time. The range may be extended upward by dilution, using a less sensitive wavelength, rotating the burner head, or utilizing a microprocessor to linearize the calibration curve at high concentrations.

5. Preparation of Standards

Prepare standard solutions of known metal concentrations in water with a matrix similar to the sample. Use standards that bracket expected sample concentration and are within the method’s working range. Very dilute standards should be prepared daily from stock solutions in concentrations greater than 500 mg/L. Stock standard solutions can be obtained from several commercial sources. They also can be prepared from National Institute of Standards and Technology (NIST, formerly National Bureau of Standards) reference materials or by procedures outlined in the following sections.
For samples containing high and variable concentrations of matrix materials, make the major ions in the sample and the dilute standard similar. If the sample matrix is complex and components cannot be matched accurately with standards, use the method of standard additions, 3113B.4d2), to correct for matrix effects. If digestion is used, carry standards through the same digestion procedure used for samples.

6. Apparatus

a. Atomic absorption spectrometer, consisting of a light source emitting the line spectrum of an element (hollow-cathode lamp or electrodeless discharge lamp), a device for vaporizing the sample (usually a flame), a means of isolating an absorption line (monochromator or filter and adjustable slit), and a photoelectric detector with its associated electronic amplifying and measuring equipment.
b. Burner: The most common type of burner is a premix, which introduces the spray into a condensing chamber for removal of large droplets. The burner may be fitted with a conventional head containing a single slot: a three-slot Boling head,

TABLE 3111:I. ATOMIC ABSORPTION CONCENTRATION RANGES WITH DIRECT ASPIRATION ATOMIC ABSORPTION

Element	Wave-length nm	Flame Gases*	Instrument Detection Limit mg/L	Sensitivity mg/L	Optimum Concentration Range mg/L
Ag	328.1	A–Ac	0.01	0.06	0.1–4
Al	309.3	N–Ac	0.1	1	5–100
Au	242.8	A–Ac	0.01	0.25	0.5–20
Ba	553.6	N–Ac	0.03	0.4	1–20
Be	234.9	N–Ac	0.005	0.03	0.05–2
Bi	223.1	A–Ac	0.06	0.4	1–50
Ca	422.7	A–Ac	0.003	0.08	0.2–20
Cd	228.8	A–Ac	0.002	0.025	0.05–2
Co	240.7	A–Ac	0.03	0.2	0.5–10
Cr	357.9	A–Ac	0.02	0.1	0.2–10
Cs	852.1	A–Ac	0.02	0.3	0.5–15
Cu	324.7	A–Ac	0.01	0.1	0.2–10
Fe	248.3	A–Ac	0.02	0.12	0.3–10
Ir	264.0	A–Ac	0.6	8	—
K	766.5	A–Ac	0.005	0.04	0.1–2
Li	670.8	A–Ac	0.002	0.04	0.1–2
Mg	285.2	A–Ac	0.0005	0.007	0.02–2
Mn	279.5	A–Ac	0.01	0.05	0.1–10
Mo	313.3	N–Ac	0.1	0.5	1–20
Na	589.0	A–Ac	0.002	0.015	0.03–1
Ni	232.0	A–Ac	0.02	0.15	0.3–10
Os	290.9	N–Ac	0.08	1	—
Pb†	283.3	A–Ac	0.05	0.5	1–20
Pt	265.9	A–Ac	0.1	2	5–75
Rh	343.5	A–Ac	0.5	0.3	—
Ru	349.9	A–Ac	0.07	0.5	—
Sb	217.6	A–Ac	0.07	0.5	1–40
Si	251.6	N–Ac	0.3	2	5–150
Sn	224.6	A–Ac	0.8	4	10–200
Sr	460.7	A–Ac	0.03	0.15	0.3–5
Ti	365.3	N–Ac	0.3	2	5–100
V	318.4	N–Ac	0.2	1.5	2–100
Zn	213.9	A–Ac	0.005	0.02	0.05–2
* A–Ac = air–acetylene; N–Ac = nitrous oxide–acetylene.
† The more sensitive 217.0 nm wavelength is recommended for instruments with background correction capabilities.
Copyright © ASTM. Reprinted with permission.

which may be preferred for direct aspiration with an air-acetylene flame: or a special head for use with nitrous oxide and acetylene.
c. Readout: Most instruments are equipped with either a digital or null meter readout mechanism. Most modern instruments are equipped with microprocessors capable of integrating absorption signals over time and linearizing the calibration curve at high concentrations.
d. Lamps: Use either a hollow-cathode lamp or an electrodeless discharge lamp (EDL). Use one lamp for each element being measured. Multi-element hollow-cathode lamps generally provide lower sensitivity than single-element lamps. EDLs take a longer time to warm up and stabilize.
e. Pressure-reducing valves: Maintain supplies of fuel and oxidant at pressures somewhat higher than the controlled operating pressure of the instrument by using suitable reducing valves. Use a separate reducing valve for each gas.
3-11f. Vent: Place a vent about 15 to 30 cm above the burner to remove fumes and vapors from the flame. This precaution protects laboratory personnel from toxic vapors, protects the instrument from corrosive vapors, and prevents flame stability from being affected by room drafts. A damper or variable-speed blower is desirable for modulating air flow and preventing flame disturbance. Select blower size to provide the air flow recommended by the instrument manufacturer. In laboratory locations with heavy particulate air pollution, use clean laboratory facilities (Section 3010C).

7. Quality Assurance/Quality Control

Some data typical of the precision and bias obtainable with the methods discussed are presented in Tables 3111:II and III.
Analyze a blank between sample or standard readings to verify baseline stability. Rezero when necessary.
To one sample out of every ten (or one sample from each group of samples if less than ten are being analyzed) add a known amount of the metal of interest and reanalyze to confirm recovery. The amount of metal added should be approximately equal to the amount found. If little metal is present add an amount close to the middle of the linear range of the test. Recovery of added metal should be between 85 and 115%.
Analyze an additional standard solution after every ten samples or with each batch of samples, whichever is less, to confirm that the test is in control. Recommended concentrations of standards to be run, limits of acceptability, and reported single-operator precision data are listed in Table 3111:III.

8. References

1. AMERICAN SOCIETY FOR TESTING AND MATERIALS, 1986. Annual Book of ASTM Standards, Volume 11.01, Water and Environmental Technology, American Soc. Testing & Materials, Philadelphia, Pa.
2. U.S. DEPARTMENT HEALTH, EDUCATION AND WELFARE, 1970. Water Metals No. 6, Study No. 37. U.S. Public Health Serv. Publ. No. 2029. Cincinnati, Ohio.
3. U.S. DEPARTMENT HEALTH, EDUCATION AND WELFARE, 1968. Water Metals No. 4, Study No. 30. U.S. Public Health Serv. Publ. No. 999-UTH-8, Cincinnati, Ohio.
4. U.S. ENVIRONMENTAL PROTECTION AGENCY, 1983. Methods for Chemical Analysis of Water and Wastes. Cincinnati, Ohio.

9. Bibliography

KAHN, H.L. 1968. Principles and Practice of Atomic Absorption. Advan Chem. Ser. No. 73, Div. Water, Air & Waste Chemistry, American Chemical Soc., Washington, D.C.
RAMIRIZ-MUNOZ, J. 1968. Atomic Absorption Spectroscopy and Analysis by Atomic Absorption Flame Photometry, American Elsevier Publishing Co., New York, N.Y.

TABLE 3111:II. INTERLABORATORY PRECISION AND BIAS DATA FOR ATOMIC ABSORPTION METHODS—DIRECT ASPIRATION AND EXTRACTED METALS

Metal	Conc. mg/L	SD mg/L	Relative SD %	Relative Error %	No. of Participants
Direct determination:
Aluminium1	4.50	0.19	4.2	8.4	5
Barium2	1.00	0.089	8.9	2.7	11
Beryllium1	0.46	0.0213	4.6	23.0	11
Cadmium3	0.05	0.0108	21.6	8.2	26
Cadmium1	1.60	0.11	6.9	5.1	16
Calcium1	5.00	0.21	4.2	0.4	8
Chromium1	3.00	0.301	10.0	3.7	9
Cobalt1	4.00	0.243	6.1	0.5	14
Copper3	1.00	0.112	11.2	3.4	53
Copper1	4.00	0.331	8.3	2.8	15
Iron1	4.40	0.260	5.8	2.3	16
Iron3	0.30	0.0495	16.5	0.6	43
Lead1	6.00	0.28	4.7	0.2	14
Magnesium3	0.20	0.021	10.5	6.3	42
Magnesium1	1.10	0.116	10.5	10.0	8
Manganese1	4.05	0.317	7.8	1.3	16
Manganese3	0.05	0.0068	13.5	6.0	14
Nickel1	3.93	0.383	9.8	2.0	14
Silver3	0.05	0.0088	17.5	10.6	7
Silver1	2.00	0.07	3.5	1.0	10
Sodium1	2.70	0.122	4.5	4.1	12
Strontium1	1.00	0.05	5.0	0.2	12
Zinc3	0.50	0.041	8.2	0.4	48
Extracted determination:
Aluminium2	300	32	10.7	0.7	15
Beryllium2	5	1.7	34.0	20.0	9
Cadmium3	50	21.9	43.8	13.3	12
Cobalt1	300	28.5	9.5	1.0	6
Copper1	100	71.7	71.7	12.0	8
Iron1	250	19.0	7.6	3.6	4
Manganese1	21.5	2.4	11.2	7.4	8
Molybdenum1	9.5	1.1	11.6	1.3	5
Nickel1	56.8	15.2	26.8	13.6	14
Lead3	50	11.8	23.5	19.0	8
Silver1	5.2	1.4	26.9	3.0	7
Source: AMERICAN SOCIETY FOR TESTING AND MATERIALS, 1986. Annual Book of ASTM Standards, Volume 11.01, Water and Environmental Technology. American Soc. Testing & Materials. Philadelphia, Pa. Copyright ASTM. Reprinted with permission.

SLAVIN, W. 1968. Atomic Absorption Spectroscopy. John Wiley & Sons. New York, N.Y.
PAUS, P.E. 1971. The application of atomic absorption spectroscopy to the analysis of natural waters. Atomic Absorption Newsletter 10:69.
EDIGER, R.D. 1973. A review of water analysis by atomic absorption. Atomic Absorption Newsletter 12:151.
PAUS, P.E. 1973. Determination of some heavy metals in seawater by atomic absorption spectroscopy. Fresenius Zeitschr Anal Chem. 264:118.
BURRELL, D.C. 1975. Atomic Spectrometric Analysis of Heavy-Metal Pollutants in Water. Ann Arbor Science Publishers, Inc., Ann Arbor, Mich.
3-12

TABLE 3111:III. SINGLE-OPERATOR PRECISION AND RECOMMENDED CONTROL RANGES FOR ATOMIC ABSORPTION METHODS—DIRECT ASPIRATION AND EXTRACTED METALS

Metal	Conc. mg/L	SD mg/L	Relative SD %	No. of Participants	QC Std. mg/L	Acceptable Range mg/L
Direct determination:
Aluminium1	4.50	0.23	5.1	15	5.00	4.3–5.7
Beryllium1	0.46	0.012	2.6	10	0.50	0.46–0.54
Calcium1	5.00	0.05	1.0	8	5.00	4.8–5.2
Chromium1	7.00	0.69	9.9	9	5.00	3.3–6.7
Cobalt1	4.00	0.21	5.3	14	4.00	3.4–4.6
Copper1	4.00	0.115	2.9	15	4.00	3.7–4.3
Iron1	5.00	0.19	3.8	16	5.00	4.4–5.6
Magnesium1	1.00	0.009	0.9	8	1.00	0.97–1.03
Nickel4	5.00	0.04	0.8	—	5.00	4.9–5.1
Silver1	2.00	0.25	12.5	10	2.00	1.2–2.8
Sodium4	8.2	0.1	1.2	—	5.00	4.8–5.2
Strontium1	1.00	0.04	4.0	12	1.00	0.87–1.13
Potassium4	1.6	0.2	12.5	—	1.6	1.0–2.2
Molybdenum4	7.5	0.07	0.9	—	10.0	9.7–10.3
Tin4	20.0	0.5	2.5	—	20.0	18.5–21.5
Titanium4	50.0	0.4	0.8	—	50.0	48.8–51.2
Vanadium	50.0	0.2	0.4	—	50.0	49.4–50.6
Extracted determination:
Aluminium1	300	12	4.0	15	300	264–336
Cobalt1	300	20	6.7	6	300	220–380
Copper1	100	21	21	8	100	22–178
Iron1	250	12	4.8	4	250	180–320
Manganese1	21.5	202	10.2	8	25	17–23
Molybdenum1	9.5	1.0	10.5	5	10	5.5–14.5
Nickel1	56.8	9.2	16.2	14	50	22–78
Silver1	5.2	1.2	23.1	7	5.0	0.5–9.5
Source: AMERICAN SOCIETY FOR TESTING AND MATERIALS, 1986. Annual Book of ASTM Standards. Volume 11.01. Water and Environmental Technology. American Soc. Testing & Materials. Philadelphia, Pa. Copyright ASTM, Reprinted with permission.

3111 B. Direct Air–Acetylene Flame Method

1. General Discussion

This method is applicable to the determination of antimony, bismuth, cadmium, calcium, cesium, chromium, cobalt, copper, gold, iridium, iron, lead, lithium, magnesium, manganese, nickel, palladium, platinum, potassium, rhodium, ruthenium, silver, sodium, strontium, thallium, tin, and zinc.

2. Apparatus

Atomic absorption spectrometer and associated equipment: See Section 3111A.6. Use burner head recommended by the manufacturer.

3. Reagents

a. Air, cleaned and dried through a suitable filter to remove oil, water, and other foreign substances. The source may be a compressor or commercially bottled gas.
b. Acetylene, standard commercial grade. Acetone, which always is present in acetylene cylinders, can be prevented from entering and damaging the burner head by replacing a cylinder when its pressure has fallen to 689 kPa (100 psi) acetylene.
c. Metal–free water: Use metal–free water for preparing all reagents and calibration standards and as dilution water. Prepare metal–free water by deionizing tap water and/or by using one of the following processes, depending on the metal concentration in the sample: single distillation, redistillation, or sub–boiling. Always check deionized or distilled water to determine whether the element of interest is present in trace amounts. (NOTE: If the source water contains Hg or other volatile metals, single– or redistilled water may not be suitable for trace analysis because these metals distill over with the distilled water. In such cases, use sub–boiling to prepare metal–free water).
d. Calcium solution: Dissolve 630 mg calcium carbonate, CaCO₃, in 50 mL of 1 + 5 HCl. If necessary, boil gently to obtain complete solution. Cool and dilute to 1000 mL with water.
e. Hydrochloric acid, HCl, 1%, 10%, 20%, 1 + 5, 1 + 1, and conc.
3-13f. Lanthanum solution: Dissolve 58.65 g lanthanum oxide, La₂O₃, in 250 mL conc HCl. Add acid slowly until the material is dissolved and dilute to 1000 mL with water.
g. Hydrogen peroxide, 30%.
h. Nitric acid, HNO₃, 2%, 1 + 1 and conc.
i. Aqua regia: Add 3 volumes conc HCl to 1 volume conc HNO₃.
j. Standard metal solutions: Prepare a series of standard metal solutions in the optimum concentration range by appropriate dilution of the following stock metal solutions with water containing 1.5 mL conc HNO₃/L. Thoroughly dry reagents before use. In general, use reagents of the highest purity. For hydrates, use fresh reagents.
1) Antimony: Dissolve 0.2669 g K (SbO)C₄H₄O₆ in water, add 10 mL 1 + 1 HCl and dilute to 1000 mL with water; 1.00 mL = 100 µg Sb.
2) Bismuth: Dissolve 0.100 g bismuth metal in a minimum volume of 1 + 1 HNO₃. Dilute to 1000 mL with 2% (v/v) HNO₃; 1.00 mL = 100 µg Bi.
3) Cadmium: Dissolve 0.100 g cadmium metal in 4 mL conc HNO₃. Add 8.0 mL, conc HNO₃ and dilute to 1000 mL with water; 1.00 mL = 100 µg Cd.
4) Calcium: Suspend 0.2497 g CaCO₃ (dried at 180° for 1 h before weighing) in water and dissolve cautiously with a minimum amount of 1 + 1 HNO₃. Add 10.0 mL conc HNO₃ and dilute to 1000 mL with water; 1.00 mL = 100 µg Ca.
5) Cesium: Dissolve 0.1267 g cesium chloride, CsCl, in 1000 mL water; 1.00 mL = 100 µg Cs.
6) Chromium: Dissolve 0.1923 g CrO₃ in water. When solution is complete, acidify with 10 mL conc HNO₃ and dilute to 1000 mL with water; 1.00 mL = 100 µg Cr.
7) Cobalt: Dissolve 0.1000g cobalt metal in a minimum amount of 1 + 1 HNO₃. Add 10.0 mL 1 + 1 HCl and dilute to 1000 mL with water; 1.00 mL = 100 µg Co.
8) Copper: Dissolve 0.100 g copper metal in 2 mL conc HNO₃, add 10.0 mL conc HNO₃ and dilute to 1000 mL with water; 1.00 mL = 100 µg Cu.
9) Gold: Dissolve 0.100 g gold metal in a minimum volume of aqua regia. Evaporate to dryness, dissolve residue in 5 mL conc HCl, cool, and dilute to 1000 mL with water: 1.00 mL = 100 µg Au.
10) Iridium: Dissolve 0.1147 g ammonium chloroiridate, (NH₄)₂ IrCl₆, in a minimum volume of 1% (v/v) HCl and dilute to 100 mL with 1% (v/v) HCl: 1.00 mL = 500 µg Ir.
11) Iron: Dissolve 0.100 g iron wire in a mixture of 10 mL 1 + 1 HCl and 3 mL conc HNO₃. Add 5 mL conc HNO₃ and dilute to 1000 mL with water: 1.00 mL = 100 µg Fe.
12) Lead: Dissolve 0.1598 g lead nitrate, Pb(NO₃)₂, in a minimum amount of 1 + 1 HNO₃, add 10 mL conc HNO₃, and dilute to 1000 mL with water; 1.00 mL = 100 µg Pb.
13) Lithium: Dissolve 0.5323 g lithium carbonate, Li₂CO₃, in a minimum volume of 1 + 1 HNO₃. Add 10.0 mL conc HNO₃ and dilute to 1000 mL with water; 1.00 mL = 100 µg Li.
14) Magnesium: Dissolve 0.1658 g MgO in a minimum amount of 1 + 1 HNO₃. Add 10.0 mL conc HNO₃ and dilute to 1000 mL with water; 1.00 mL = 100 µg Mg.
15) Manganese: Dissolve 0.1000 g manganese metal in 10 mL conc HCl mixed with 1 mL conc HNO₃. Dilute to 1000 mL with water; 1.00 mL = 100 µg Mn.
16) Nickel: Dissolve 0.1000 g nickel metal in 10 mL hot conc HNO₃, cool, and dilute to 1000 mL with water: 1.00 mL = 100 µg Ni.
17) Palladium: Dissolve 0.100 g palladium wire in a minimum volume of aqua regia and evaporate just to dryness. Add 5 mL conc HCl and 25 mL water and warm until dissolution is complete. Dilute to 1000 mL with water; 1.00 mL = 100 µg Pd.
18) Platinum: Dissolve 0.100 g platinum metal in a minimum volume of aqua regia and evaporate just to dryness. Add 5 mL. conc HCl and 0.1 g NaCl and again evaporate just to dryness. Dissolve residue in 20 mL of 1 + 1 HCl and dilute to 1000 mL with water; 1.00 mL = 100 µg Pt.
19) Potassium: Dissolve 0.1907 g potassium chloride. KCl. (dried at 110°C) in water and make up to 1000 mL: 1.00 mL = 100 µg K.
20) Rhodium: Dissolve 0.386 g ammonium hexachlororhodate. (NH₄)₃RhCl₆· 1.5H₂O, in a minimum volume of 10% (v/v) HCl and dilute to 1000 mL with 10% (v/v) HCl; 1.00 mL = 100 µg Rh.
21) Ruthenium: Dissolve 0.205 g ruthenium chloride, RuCl₃ in a minimum volume of 20% (v/v) HCl and dilute to 1000 mL with 20% (v/v) HCl; 1.00 mL = 100 µg Ru.
22) Silver: Dissolve 0.1575 g silver nitrate, AgNO₃, in 100 mL water, add 10 mL conc HNO₃, and make up to 1000 mL: 1.00 mL = 100 µg Ag.
23) Sodium: Dissolve 0.2542 g sodium chloride, NaCl, dried at 140°C, in water, add 10 mL cone HNO₃ and make up to 1000 mL: 1.00 mL =100 µg Na.
24) Strontium: Suspend 0.1685 g SrCO₃ in water and dissolve cautiously with a minimum amount of 1 + 1 HNO₃. Add 10.0 mL conc HNO₃ and dilute to 1000 mL with water: 1 mL = 100 µg Sr.
25) Thallium: Dissolve 0.1303 g thallium nitrate. TINO₃, in water. Add 10 mL cone HNO₃ and dilute to 1000 mL with water; 1.00 mL = 100 µg Tl.
26) Tin: Dissolve 1.000 g tin metal in 100 mL conc HCI and dilute to 1000 mL with water; 1.00 mL = 1.00 mg Sn.
27) Zinc: Dissolve 0.100 g zine metal in 20 mL 1 + 1 HCI and dilute to 1000 mL with water: 1.00 mL = 100 µg Zn.

4. Procedure

a. Sample preparation: Required sample preparation depends on need to measure dissolved metals only or total metals.
If dissolved metals are to be determined, see Section 3030B for sample preparation. If total or acid-extractable metals are to be determined, see Sections 3030C through K. For all samples, make certain that the concentrations of acid and matrix modifiers are the same in both samples and standards.
When determining Ca or Mg, dilute and mix 100 mL sample or standard with 10 mL lanthanum solution (¶ 3f) before atomization. When determining Fe or Mn, mix 100 mL with 25 mL of Ca solution (¶ 3d) before aspirating. When determining Cr, mix 1 mL 30% H₂O₂ with each 100 mL before aspirating. Alternatively use proportionally smaller volumes.
b. Instrument operation: Because of differences between makes and models of atomic absorption spectrometers, it is not possible to formulate instructions applicable to every instrument. See manufacturer’s operating manual. In general proceed according to the following: Install a hollow-cathode lamp for the desired
3-14metal in the instrument and roughly set the wavelength dial according to Table 3111:I. Set slit width according to manufacturer’s suggested setting for the element being measured. Turn on instrument, apply to the hollow-cathode lamp the current suggested by the manufacturer, and let instrument warm up until energy source stabilizes, generally about 10 to 20 min. Readjust current as necessary after warmup. Optimize wavelength by adjusting wavelength dial until optimum energy gain is obtained. Align lamp in accordance with manufacturer’s instructions.
Install suitable burner head and adjust burner head position. Turn on air and adjust flow rate to that specified by manufacturer to give maximum sensitivity for the metal being measured. Turn on acetylene, adjust flow rate to value specified, and ignite flame. Let flame stabilize for a few minutes. Aspirate a blank consisting of either deionized water or an acid solution containing the same concentration of acid in standards and samples. Zero the instrument. Aspirate a standard solution and adjust aspiration rate of the nebulizer to obtain maximum sensitivity. Adjust burner both vertically and horizontally to obtain maximum response. Aspirate blank again and rezero the instrument. Aspirate a standard near the middle of the linear range. Record absorbance of this standard when freshly prepared and with a new hollow-cathode lamp. Refer to these data on subsequent determinations of the same element to check consistency of instrument setup and aging of hollow-cathode lamp and standard.
The instrument now is ready to operate. When analyses are finished, extinguish flame by turning off first acetylene and then air.
c. Standardization: Select at least three concentrations of each standard metal solution (prepared as in ¶ 3j above) to bracket the expected metal concentration of a sample. Aspirate blank and zero the instrument. Then aspirate each standard in turn into flame and record absorbance.
Prepare a calibration curve by plotting on linear graph paper absorbance of standards versus their concentrations. For instruments equipped with direct concentration readout, this step is unnecessary. With some instruments it may be necessary to convert percent absorption to absorbance by using a table generally provided by the manufacturer. Plot calibration curves for Ca and Mg based on original concentration of standards before dilution with lanthanum solution. Plot calibration curves for Fe and Mn based on original concentration of standards before dilution with Ca solution. Plot calibration curve for Cr based on original concentration of standard before addition of H₂O₂.
d. Analysis of samples: Rinse nebulizer by aspirating water containing 1.5 mL conc HNO₃/L. Atomize blank and zero instrument. Atomize sample and determine its absorbance.

5. Calculations

Calculate concentration of each metal ion, in micrograms per liter for trace elements, and in milligrams per liter for more common metals, by referring to the appropriate calibration curve prepared according to ¶ 4c. Alternatively, read concentration directly from the instrument readout if the instrument is so equipped. If the sample has been diluted, multiply by the appropriate dilution factor.

6. Bibliography

WILLIS, J.B. 1962. Determination of lead and other heavy metals in urine by atomic absorption spectrophotometry. Anal, Chem. 34:614.
Also see Section 3111A.8 and 9.

3111 C. Extraction/Air-Acetylene Flame Method

1. General Discussion

This method is suitable for the determination of low concentrations of cadmium, chromium, cobalt, copper, iron, lead, manganese, nickel, silver, and zinc. The method consists of chelation with ammonium pyrrolidine dithiocarbamate (APDC) and extraction into methyl isobutyl ketone (MIBK) followed by aspiration into an air-acetylene flame.

2. Apparatus

a. Atomic absorption spectrometer and associated equipment: See Section 3111A.6.
b. Burner head, conventional. Consult manufacturer’s operating manual for suggested burner head.

3. Reagents

a. Air: See 3111B.3a.
b. Acetylene: See 3111B.3b.
c. Metal-free water: See 3111B. 3c.
d. Methyl isobutyl ketone (MIBK), reagent grade. For trace analysis, purify. MIBK by redistillation or by sub-boiling distillation.
e. Ammonium pyrrolidine dithiocarbamate (APDC) solution: Dissolve 4 g APDC in 100 mL water. If necessary, purify APDC with an equal volume of MIBK. Shake 30 s in a separatory funnel, let separate, and withdraw lower portion. Discard MIBK layer.
f. Nitric acid, HNO₃, cone, ultrapure.
g. Standard metal solutions: See 3111B. 3j.
h. Potassium permanganate solution, KMnO₄, 5% aqueous.
i. Sodium sulfate, Na₂SO₄, anhydrous.
j. Water-saturated MIBK: Mix one part purified MIBK with one part water in a separatory funnel. Shake 30 s and let separate. Discard aqueous layer. Save MIBK layer.
k. Hydroxylamine hydrochloride solution, 10%.

4. Procedure

a. Instrument operation: See Section 3111B.4b. After final adjusting of burner position, aspirate water-saturated MIBK into flame and gradually reduce fuel flow until flame is similar to that
3-15before aspiration of solvent.
b. Standardization: Select at least three concentrations of standard metal solutions (prepared as in 3111B.3j) to bracket expected sample metal concentration and to be, after extraction, in the optimum concentration range of the instrument. Adjust 100 mL of each standard and 100 mL of a metal-free water blank to pH 3 by adding 1NHNO₃ or 1N NaOH. For individual element extraction, use the following pH ranges to obtain optimum extraction efficiency:

Element	pH Range for Optimum Extraction
Ag	2—5 (complex unstable)
Cd	1—6
Co	2—10
Cr	3—9
Cu	0.1—8
Fe	2—5
Mn	2—4 (complex unstable)
Ni	2—4
Pb	0.1—6
Zn	2—6

NOTE: For Ag and Pb extraction the optimum pH value is 2.3 plusmn; 0.2. The Mn complex deteriorates rapidly at room temperature, resulting in decreased instrument response. Chilling the extract to 0°C may preserve the complex for a few hours. If this is not possible and Mn cannot be analyzed immediately after extraction, use another analytical procedure.
Transfer each standard solution and blank to individual 200-mL volumetric flasks, add 1 mL APDC solution, and shake to mix. Add 10 mL MIBK and shake vigorously for 30 s. (The maximum volume ratio of sample to MIBK is 40.) Let contents of each flask separate into aqueous and organic layers, then carefully add water (adjusted to the same pH at which the extraction was carried out) down the side of each flask to bring the organic layer into the neck and accessible to the aspirating tube.
Aspirate organic extracts directly into the flame (zeroing instrument on a water-saturated MIBK blank) and record absorbance.
Prepare a calibration curve by plotting on linear graph paper absorbances of extracted standards against their concentrations before extraction.
c. Analysis of samples: Prepare samples in the same manner as the standards. Rinse atomizer by aspirating water-saturated MIBK. Aspirate organic extracts treated as above directly into the flame and record absorbances.
With the above extraction procedure only hexavalent chromium is measured. To determine total chromium oxidize trivalent chromium to hexavalent chromium by bringing sample to a boil and adding sufficient KMnO₄ solution dropwise to give a persistent pink color while the solution is boiled for 10 min. Destroy excess KMnO₄ by adding 1 to 2 drops hydroxylamine hydrochloride solution to the boiling solution, allowing 2 min for the reaction to proceed. If pink color persists, add 1 to 2 more drops hydroxylamine hydrochloride solution and wait 2 min. Heat an additional 5 min. Cool, extract with MIBK, and aspirate.
During extraction, if an emulsion forms at the water-MIBK interface, add anhydrous Na₂SO₄ to obtain a homogeneous organic phase. In that case, also add Na₂SO₄ to all standards and blanks.
To avoid problems associated with instability of extracted metal complexes, determine metals immediately after extraction.

5. Calculations

Calculate the concentration of each metal ion in micrograms per liter by referring to the appropriate calibration curve.

6. Bibliography

ALLAN, J.E. 1961. The use of organic solvents in atomic absorption spectrophotometry. Spectrochim. Acta 17:467.
SACHDEV, S.L. & P.W. WEST. 1970. Concentration of trace metals by solvent extraction and their determination by atomic absorption spectrophotometry. Environ. Sci. Technol. 4:749.

3111 D. Direct Nitrous Oxide-Acetylene Flame Method

1. General Discussion

This method is applicable to the determination of aluminum, barium, beryllium, molybdenum, osmium, rhenium, silicon, thorium, titanium, and vanadium.

2. Apparatus

a. Atomic absorption spectrometer and associated equipment: See Section 3111A.6.
b. Nitrous oxide burner head: Use special burner head as suggested in manufacturer’s manual. At roughly 20-min intervals of operation it may be necessary to dislodge the carbon crust that forms along the slit surface with a carbon rod or appropriate alternative.
c. T-junction valve or other switching valve for rapidly changing from nitrous oxide to air, so that flame can be turned on or off with air as oxidant to prevent flashbacks.

3. Reagents

a. Air: See 3111B.3a.
b. Acetylene: See 3111B.3b.
c. Metal-free water: See 3111B.3c.
d. Hydrochloric acid, HCl, 1N, 1+1, and conc.
e. Nitric acid, HNO₃, conc.
f. Sulfuric acid, H₂SO₄, 1%.
g. Hydrofluoric acid, HF, 1N.
h. Nitrous oxide, commercially available cylinders. Fit nitrous oxide cylinder with a special nonfreezable regulator or wrap a
3-16heating coil around an ordinary regulator to prevent flashback at the burner caused by reduction in nitrous oxide flow through a frozen regulator. (Some atomic absorption instruments have automatic gas control systems that will shut down a nitrous oxideacetylene flame safely in the event of a reduction in nitrous oxide flow rate.)
i. Potassium chloride solution: Dissolve 250 g KCl in water and dilute to 1000 mL.
j. Aluminum nitrate solution: Dissolve 139 g Al(NO₃)₃ 9H₂O in 150 mL water. Acidify slightly with conc HNO₃ to preclude possible hydrolysis and precipitation. Warm to dissolve completely. Cool and dilute to 200 mL.
k. Standard metal solutions: Prepare a series of standard metal solutions in the optimum concentration ranges by appropriate dilution of the following stock metal solutions with water containing 1.5 mL conc HNO₃/L:
1) Aluminum: Dissolve 0.100 g aluminum metal in an acid mixture of 4 mL 1 + 1 HCl and 1 mL conc HNO₃ in a beaker. Warm gently to effect solution. Transfer to a 1-L flask, add 10 mL 1 + 1 HCl, and dilute to 1000 mL with water; 1.00 mL = 100 µg Al.
2) Barium: Dissolve 0.1516 g BaCl₂ (dried at 250° for 2 h), in about 10 mL water with 1 mL 1 + 1 HCl. Add 10.0 mL 1 + 1 HCl and dilute to 1000 mL with water: 1.00 mL = 100 µg Ba.
3) Beryllium: Do not dry. Dissolve 1.966 g BeSO₄-4H₂O in water, add 10.0 mL conc HNO₃, and dilute to 1000 mL with water; 1.00 mL = 100 µg Be.
4) Molybdenum: Dissolve 0.2043 g (NH₄)₂MoO₄ in water and dilute to 1000 mL; 1.00 mL = 100 µg Mo.
5) Osmium: Obtain standard 0.1M osmium tetroxide solution^* and store in glass bottle; 1.00 mL = 19.02 mg Os. Make dilutions daily as needed using 1% (v/v) H₂SO₄ CAUTION: OsO₄ is extremely toxic and highly volatile.
6) Rhenium: Dissolve 0.1554 g potassium perrhenate, KReO₄, in 200 mL water. Dilute to 1000 mL with 1% (v/v) H₂SO₄: 1.00 mL = 100 µg Re.
7) Silica: Do not dry. Dissolve 0.4730 g Na₂SiO₃ 9H₂O in water. Add 10.0 mL conc HNO₃ and dilute to 1000 mL with water. 1.00 mL = 100 µg Si. Store in polyethylene.
8) Thorium: Dissolve 0.238 g thorium nitrate, Th(NO₃)₄ 4H₂O in 1000 mL water; 1.00 mL = 100 µg Th.
9) Titanium: Dissolve 0.3960 g pure (99.8 or 99.9%) titanium chloride. TiCl₄, † in a mixture of equal volumes of 1N HCl and 1N HF. Make up to 1000 mL with this acid mixture; 1.00 mL = 100 µg Ti.
10) Vanadium: Dissolve 0.2297 g ammonium metavanadate, NH₄VO₃, in a minimum amount of conc HNO₃. Heat to dissolve. Add 10 mL conc HNO₃, and dilute to 1000 mL with water; 1.00 mL = 100 µg V.

4. Procedure

a. Sample preparation: See Section 3111B.4a.
b. Instrument operation: See Section 3111B.4b. After adjusting wavelength, install a nitrous oxide burner head. Turn on acetylene (without igniting flame) and adjust flow rate to value specified by manufacturer for a nitrous oxide-acetylene flame. Turn off acetylene. With both air and nitrous oxide supplies turned on, set T-junction valve to nitrous oxide and adjust flow rate according to manufacturer’s specifications. Turn switching valve to the air position and verify that flow rate is the same. Turn acetylene on and ignite to a bright yellow flame. With a rapid motion, turn switching valve to nitrous oxide. The flame should have a red cone above the burner. If it does not, adjust fuel flow to obtain red cone. After nitrous oxide flame has been ignited, let burner come to thermal equilibrium before beginning analysis.
Atomize water containing 1.5 mL conc HNO₃/L and check aspiration rate. Adjust if necessary to a rate between 3 and 5 mL/min. Atomize a standard of the desired metal with a concentration near the midpoint of the optimum concentration range and adjust burner (both horizontally and vertically) in the light path to obtain maximum response. The instrument now is ready to run standards and samples.
To extinguish flame, turn switching valve from nitrous oxide to air and turn off acetylene. This procedure eliminates the danger of flashback that may occur on direct ignition or shutdown of nitrous oxide and acetylene.
c. Standardization: Select at least three concentrations of standard metal solutions (prepared as in ¶ 3k) to bracket the expected metal concentration of a sample. Aspirate each in turn into the flame. Record absorbances. For Al, Ba, and Ti, add 2 mL KCl solution to 100 mL standard before aspiration. For Mo and V add 2 mL Al(NO₃)₃ 9H₂O solution to 100 mL standard before aspiration.
Most modern instruments are equipped with microprocessors and digital readout which permit calibration in direct concentration terms. If instrument is not so equipped, prepare a calibration curve by plotting on linear graph paper absorbance of standards versus concentration. Plot calibration curves for Al, Ba, and Ti based on original concentration of standard before adding KCl solution. Plot calibration curves for Mo and V based on original concentration of standard before adding Al(NO₃)₃ solution.
d. Analysis of samples: Rinse atomizer by aspirating water containing 1.5 mL conc HNO₃/L and zero instrument. Atomize a sample and determine its absorbance.
When determining Al, Ba, and Ti, add 2 mL KCl solution to 100 mL sample before atomization. For Mo and V. add 2 mL Al(NO₃)₃ 9H₂O solution to 100 mL sample before atomization.

5. Calculations

Calculate concentration of each metal ion in micrograms per liter by referring to the appropriate calibration curve prepared according to ¶ 4c.
Alternatively, read the concentration directly from the instrument readout if the instrument is so equipped. If sample has been diluted, multiply by the appropriate dilution factor.

6. Bibliography

WILLIS. J.B. 1965. Nitrous oxide-acetylene flame in atomic absorption spectroscopy. Nature 207:715.
Also see Section 3111A.8 and 9.
^* GFS Chemical Co., P.O. Box 23214. Columbus. Ohio 43223. Cat. No. 64, or equivalent.
† Alpha Ventron. P.O. Box 299. 152 Andover St., Danvers, Mass. 01923, or equivalent.
3-17

3111 E. Extraction/Nitrous Oxide-Acetylene Flame Method

1. General Discussion

a. Application: This method is suitable for the determination of aluminum at concentrations less than 900 µg/L and beryllium at concentrations less than 30 µg/L. The method consists of chelation with 8-hydroxyquinoline, extraction with methyl isobutyl ketone (MIBK), and aspiration into a nitrous oxide-acetylene flame.
b. Interferences: Concentrations of Fe greater than 10 mg/L interfere by suppressing Al absorption. Iron interference can be masked by addition of hydroxylamine hydrochloride/1,10-phenanthroline. Mn concentrations up to 80 mg/L do not interfere if turbidity in the extract is allowed to settle. Mg forms an insoluble chelate with 8-hydroxyquinoline at pH 8.0 and tends to remove Al complex as a coprecipitate. However, the Mg complex forms slowly over 4 to 6 min; its interference can be avoided if the solution is extracted immediately after adding buffer.

2. Apparatus

Atomic absorption spectrometer and associated equipment: See Section 3111A.6.

3. Reagents

a. Air: See 3111B.3a.
b. Acetylene: See 3111B.3b.
c. Ammonium hydroxide, NH₄OH, conc.
d. Buffer: Dissolve 300 g ammonium acetate. NH₄C₂H₃O₂, in water, add 105 mL conc NH₄OH, and dilute to 1 L.
e. Metal-free water: See 3111B.2c.
f. Hydrochloric ac