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 Committee, 2009. Editorial revisions, 2011.

3112 B. Cold-Vapor Atomic Absorption Spectrometric Method

1. General Discussion 3. Reagents†

This method is applicable to the determination of mercury. a. Metal-free water: See Section 3111B.3c.
The QC practices considered to be an integral part of each b. Stock mercury solution: Dissolve 0.1354 g mercuric chlo-
method can be found in Section 3020. ride, HgCl2, in about 70 mL water, add 1 mL conc HNO3, and
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 measuring mercury via the cold vapor technique are water and dilute to 1 L.
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 䡠 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) below, or stannous sulfate, ¶ 2) below, to prepare this
c. Cell support: Strap cell to the flat nitrous-oxide burner head solution containing 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 an air flow of 2 L/min. Any other and dilute to 100 mL.
regulated compressed air system or air cylinder also is satisfac- Both solutions decompose with aging. If a suspension forms,
tory. stir reagent continuously during use. Reagent volume is suffi-
e. Flowmeter, capable of measuring an air flow of 2 L/min. cient to process about 20 samples; adjust volumes prepared to
f. Aeration tubing, a straight glass frit having a coarse porosity accommodate number of samples processed.
for use in reaction flask. i. Sulfuric acid, H2SO4, conc.
g. Reaction flask, 250-mL erlenmeyer flask or a BOD bottle,
fitted with a rubber stopper to hold aeration tube. 4. Procedure
h. Drying tube, 150-mm ⫻ 18-mm-diam, containing 20 g Mg
a. Instrument operation: See Section 3111B.4b. Set wavelength
(ClO4)2. A 60-W light bulb with a suitable shade may be sub-
to 253.7 nm. Install absorption cell and align in light path to give
stituted to prevent condensation of moisture inside the absorp-
maximum transmission. Connect associated equipment to absorp-
tion cell. Position bulb to maintain cell temperature at 10°C
tion cell with glass or vinyl plastic tubing, as indicated in Figure
above ambient.
3112:1. Turn on air and adjust flow rate to 2 L/min. Allow air to
i. Connecting tubing, glass tubing to pass mercury vapor from
flow continuously. Alternatively, follow manufacturer’s directions
reaction flask to absorption cell and to interconnect all other com-
for operation. NOTE: Fluorescent lighting may increase baseline
ponents. Clear vinyl plastic tubing* may be substituted for glass.
noise.

* Tygon, or equivalent. † Use specially prepared reagents low in mercury.

1
 COLD-VAPOR ATOMIC ABSORPTION SPECTROMETRY (3112)/Cold-Vapor Atomic Absorption Spectrometric Method

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

separate tube and frit to avoid carryover of residual stannous

chloride, which could cause reduction and loss of mercury.

5. Calculation

Determine peak height of sample from recorder chart and read

mercury value from standard curve prepared according to
3112B.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”
Figure 3112:1. Schematic arrangement of equipment for measuring method for determining mercury. J. Amer. Water Works Assoc.
mercury by cold-vapor atomic absorption technique. 64:20.

8. Bibliography
b. Standardization: Transfer 100 mL each of the 1.0, 2.0, and
HATCH, W.R. & W.L. OTT. 1968. Determination of submicrogram quan-
5.0 ␮g/L Hg standard solutions and a blank of 100 mL water to
tities of mercury by atomic absorption spectrophotometry. Anal.
250-mL erlenmeyer reaction flasks. Add 5 mL conc H2SO4 and Chem. 40:2085.
2.5 mL conc HNO3 to each flask. Add 15 mL KMnO4 solution UTHE, J.F., F.A.J. ARMSTRONG & M.P. STAINTON. 1970. Mercury deter-
to each flask and let stand at least 15 min. Add 8 mL K2S2O8 mination in fish samples by wet digestion and flameless atomic
solution to each flask and heat for 2 h in a water bath at 90 to absorption spectrophotometry. J. Fish. Res. Board Can. 27:805.
95°C. Cool to room temperature. FELDMAN, C. 1974. Preservation of dilute mercury solutions. Anal.
Treating each flask individually, add enough NaCl-hydroxyl- Chem. 46:99.
amine solution to reduce excess KMnO4, then add 5 mL SnCl2 BOTHNER, M.H. & D.E. ROBERTSON. 1975. Mercury contamination of sea
or SnSO4 solution and immediately attach flask to aeration water samples stored in polyethylene containers. Anal. Chem. 47:
apparatus. As Hg is volatilized and carried into the absorption 592.
HAWLEY, J.E. & J.D. INGLE, JR. 1975. Improvements in cold vapor atomic
cell, absorbance will increase to a maximum within a few sec-
absorption determination of mercury. Anal. Chem. 47:719.
onds. As soon as recorder returns approximately to the baseline, LO, J.M. & C.M. WAL. 1975. Mercury loss from water during storage:
remove stopper holding the frit from reaction flask, and replace Mechanisms and prevention. Anal. Chem. 47:1869.
with a flask containing water. Flush system for a few seconds, EL-AWADY, A.A., R.B. MILLER & M.J. CARTER. 1976. Automated method
and run the next standard in the same manner. Construct a for the determination of total and inorganic mercury in water and
standard curve by plotting peak height versus micrograms Hg. wastewater samples. Anal. Chem. 48:110.
c. Analysis of samples: Transfer 100 mL sample or portion ODA, C.E. & J.D. INGLE, JR. 1981. Speciation of mercury by cold vapor
diluted to 100 mL containing not more than 5.0 ␮g Hg/L to a atomic absorption spectrometry with selective reduction. Anal.
reaction flask. Treat as in 3112B.4b. Seawaters, brines, and Chem. 53:2305.
effluents high in chlorides require as much as another 25 mL SUDDENDORF, R.F. 1981. Interference by selenium or tellurium in the
determination of mercury by cold vapor generation atomic absorp-
KMnO4 solution. During oxidation step, chlorides are converted
tion spectrometry. Anal. Chem. 53:2234.
to free chlorine, which absorbs at 253 nm. Remove all free HEIDEN, R.W. & D.A. AIKENS. 1983. Humic acid as a preservative for
chlorine before the Hg is reduced and swept into the cell by trace mercury (II) solutions stored in polyolefin containers. Anal.
using an excess (25 mL) of hydroxylamine reagent. Chem. 55:2327.
Remove free chlorine by sparging sample gently with air or CHOU, H.N. & C.A. NALEWAY. 1984. Determination of mercury by cold
nitrogen after adding hydroxylamine reducing solution. Use a vapor atomic absorption spectrometry. Anal. Chem. 56:1737.