COLD-VAPOR ATOMIC ABSORPTION SPECTROMETRY (3112)/Cold-Vapor Atomic Absorption Spectrometric Method 3-23

3112 METALS BY COLD-VAPOR ATOMIC ABSORPTION SPECTROMETRY*

3112 A. Introduction

For general introductory material on atomic absorption spec-

trometric methods, see Section 3111A.

* Approved by Standard Methods Commitee, 1999.

3112 B. Cold-Vapor Atomic Absorption Spectrometric Method

1. General Discussion b. Stock mercury solution: Dissolve 0.1354 g mercuric chlo-

ride, HgCl2, in about 70 mL water, add 1 mL conc HNO3, and
This method is applicable to the determination of mercury. dilute to 100 mL with water; 1.00 mL 1.00 mg Hg.
c. Standard mercury solutions: Prepare a series of standard
2. Apparatus mercury solutions containing 0 to 5 g/L by appropriate dilution
of stock mercury solution with water containing 10 mL conc
When possible, dedicate glassware for use in Hg analysis. HNO3/L. Prepare standards daily.
Avoid using glassware previously exposed to high levels of Hg, d. Nitric acid, HNO3, conc.
such as those used in COD, TKN, or Cl analysis. e. Potassium permanganate solution: Dissolve 50 g KMnO4 in
a. Atomic absorption spectrometer and associated equipment: water and dilute to 1 L.
See Section 3111A.6. Instruments and accessories specifically f. Potassium persulfate solution: Dissolve 50 g K2S2O8 in
designed for measurement of mercury by the cold vapor tech- water and dilute to 1 L.
nique are available commercially and may be substituted. g. Sodium chloride-hydroxylamine sulfate solution: Dissolve
b. Absorption cell, a glass or plastic tube approximately 2.5 cm in 120 g NaCl and 120 g (NH2OH)2 H2SO4 in water and dilute to
diameter. An 11.4-cm-long tube has been found satisfactory but a 1 L. A 10% hydroxylamine hydrochloride solution may be
15-cm-long tube is preferred. Grind tube ends perpendicular to the substituted for the hydroxylamine sulfate.
longitudinal axis and cement quartz windows in place. Attach gas h. Stannous ion (Sn2) solution: Use either stannous chloride,
inlet and outlet ports (6.4 mm diam) 1.3 cm from each end. 1), or stannous sulfate, 2), to prepare this solution containing
c. Cell support: Strap cell to the flat nitrous-oxide burner head about 7.0 g Sn2/100 mL.
or other suitable support and align in light beam to give maxi- 1) Dissolve 10 g SnCl2 in water containing 20 mL conc HCl
mum transmittance. and dilute to 100 mL.
d. Air pumps: Use any peristaltic pump with electronic speed 2) Dissolve 11 g SnSO4 in water containing 7 mL conc H2SO4
control capable of delivering 2 L air/min. Any other regulated and dilute to 100 mL.
compressed air system or air cylinder also is satisfactory. Both solutions decompose with aging. If a suspension forms,
e. Flowmeter, capable of measuring an air flow of 2 L/min. stir reagent continuously during use. Reagent volume is suffi-
f. Aeration tubing, a straight glass frit having a coarse porosity cient to process about 20 samples; adjust volumes prepared to
for use in reaction flask. accommodate number of samples processed.
g. Reaction flask, 250-mL erlenmeyer flask or a BOD bottle, i. Sulfuric acid, H2SO4, conc.
fitted with a rubber stopper to hold aeration tube.
h. Drying tube, 150-mm 18-mm-diam, containing 20 g Mg
(ClO4)2. A 60-W light bulb with a suitable shade may be sub- 4. Procedure
stituted to prevent condensation of moisture inside the absorp-
tion cell. Position bulb to maintain cell temperature at 10C a. Instrument operation: See Section 3111B.4b. Set wavelength to
above ambient. 253.7 nm. Install absorption cell and align in light path to give maxi-
i. Connecting tubing, glass tubing to pass mercury vapor from mum transmission. Connect associated equipment to absorption cell
reaction flask to absorption cell and to interconnect all other com- with glass or vinyl plastic tubing as indicated in Figure 3112:1. Turn on
ponents. Clear vinyl plastic* tubing may be substituted for glass. air and adjust flow rate to 2 L/min. Allow air to flow continuously.
Alternatively, follow manufacturers directions for operation. NOTE:
3. Reagents Fluorescent lighting may increase baseline noise.
b. Standardization: Transfer 100 mL of each of the 1.0, 2.0,
a. Metal-free water: See 3111B.3c. and 5.0 g/L Hg standard solutions and a blank of 100 mL water
to 250-mL erlenmeyer reaction flasks. Add 5 mL conc H2SO4
* Tygon or equivalent. and 2.5 mL conc HNO3 to each flask. Add 15 mL KMnO4
Use specially prepared reagents low in mercury. solution to each flask and let stand at least 15 min. Add 8 mL
3-24 METALS (3000)

TABLE 3112:I. INTERLABORATORY PRECISION AND BIAS OF COLD-VAPOR

ATOMIC ABSORPTION SPECTROMETRIC METHOD FOR MERCURY1
Relative Relative
Conc. SD SD Error No. of
Form g/L g/L % % Participants

Inorganic 0.34 0.077 22.6 21.0 23

Inorganic 4.2 0.56 13.3 14.4 21
Organic 4.2 0.36 8.6 8.4 21

5. Calculation

Determine peak height of sample from recorder chart and read

mercury value from standard curve prepared according to 4b.

6. Precision and Bias

Data on interlaboratory precision and bias for this method are

given in Table 3112:I.

7. Reference

1. KOPP, J.F., M.C. LONGBOTTOM & L.B. LOBRING. 1972. Cold vapor
method for determining mercury. J. Amer. Water Works Assoc.
64:20.

Figure 3112:1. Schematic arrangement of equipment for measurement 8. Bibliography

of mercury by cold-vapor atomic absorption technique.
HATCH, W.R. & W.L. OTT. 1968. Determination of submicrogram quan-
tities of mercury by atomic absorption spectrophotometry. Anal.
Chem. 40:2085.
K2S2O8 solution to each flask and heat for 2 h in a water bath at UTHE, J.F., F.A.J. ARMSTRONG & M.P. STAINTON. 1970. Mercury deter-
95C. Cool to room temperature. mination in fish samples by wet digestion and flameless atomic
Treating each flask individually, add enough NaCl-hydroxyl- absorption spectrophotometry. J. Fish. Res. Board Can. 27:805.
amine solution to reduce excess KMnO4, then add 5 mL SnCl2 FELDMAN, C. 1974. Preservation of dilute mercury solutions. Anal.
or SnSO4 solution and immediately attach flask to aeration Chem. 46:99.
apparatus. As Hg is volatilized and carried into the absorption BOTHNER, M.H. & D.E. ROBERTSON. 1975. Mercury contamination of sea
cell, absorbance will increase to a maximum within a few sec- water samples stored in polyethylene containers. Anal. Chem. 47:
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HAWLEY, J.E. & J.D. INGLE, JR. 1975. Improvements in cold vapor atomic
remove stopper holding the frit from reaction flask, and replace
absorption determination of mercury. Anal. Chem. 47:719.
with a flask containing water. Flush system for a few seconds LO, J.M. & C.M. WAL. 1975. Mercury loss from water during storage:
and run the next standard in the same manner. Construct a Mechanisms and prevention. Anal. Chem. 47:1869.
standard curve by plotting peak height versus micrograms Hg. EL-AWADY, A.A., R.B. MILLER & M.J. CARTER. 1976. Automated method
c. Analysis of samples: Transfer 100 mL sample or portion for the determination of total and inorganic mercury in water and
diluted to 100 mL containing not more than 5.0 g Hg/L to a wastewater samples. Anal. Chem. 48:110.
reaction flask. Treat as in 4b. Seawaters, brines, and effluents ODA, C.E. & J.D. INGLE, JR. 1981. Speciation of mercury by cold vapor
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solution. During oxidation step, chlorides are converted to free Chem. 53:2305.
chlorine, which absorbs at 253 nm. Remove all free chlorine SUDDENDORF, R.F. 1981. Interference by selenium or tellurium in the
determination of mercury by cold vapor generation atomic absorp-
before the Hg is reduced and swept into the cell by using an
tion spectrometry. Anal. Chem. 53:2234.
excess (25 mL) of hydroxylamine reagent. HEIDEN, R.W. & D.A. AIKENS. 1983. Humic acid as a preservative for
Remove free chlorine by sparging sample gently with air or trace mercury (II) solutions stored in polyolefin containers. Anal.
nitrogen after adding hydroxylamine reducing solution. Use a Chem. 55:2327.
separate tube and frit to avoid carryover of residual stannous CHOU, H.N. & C.A. NALEWAY. 1984. Determination of mercury by cold
chloride, which could cause reduction and loss of mercury. vapor atomic absorption spectrometry. Anal. Chem. 56:1737.