3-106 METALS (3000)

3500-Zn ZINC*
3500-Zn A. Introduction

1. Occurrence and Significance standard MCL is 5 mg/L. Concentrations above 5 mg/L can
cause a bitter astringent taste and an opalescence in alkaline
Zinc (Zn) is the first element in Group IIB in the periodic waters. Zinc most commonly enters the domestic water supply
table; it has an atomic number of 30, an atomic weight of 65.38, from deterioration of galvanized iron and dezincification of
and a valence of 2. The average abundance of Zn in the earth’s brass. In such cases lead and cadmium also may be present
crust is 76 ppm; in soils it is 25 to 68 ppm; in streams it is 20 because they are impurities of the zinc used in galvanizing. Zinc
␮g/L, and in groundwaters it is ⬍0.1 mg/L. The solubility of in water also may result from industrial waste pollution.
zinc is controlled in natural waters by adsorption on mineral
surfaces, carbonate equilibrium, and organic complexes. Zinc is 2. Selection of Method
used in a number of alloys such as brass and bronze, and in
batteries, fungicides, and pigments. Zinc is an essential growth The atomic absorption spectrometric methods (3111B and C)
element for plants and animals but at elevated levels it is toxic to and inductively coupled plasma methods (3120 and 3125) are
some species of aquatic life. The United Nations Food and preferred. The zincon method (B), suitable for analysis of both
Agriculture Organization recommended level for zinc in irriga- potable and polluted waters, may be used if instrumentation for
tion waters is 2 mg/L. The U.S. EPA secondary drinking water the preferred methods is not available.
3. Sampling and Storage
* Approved by Standard Methods Committee, 1997.
Joint Task Group: 20th Edition—See 3500-Al. See Section 3010B.2 for sample handling and storage.

3500-Zn B. Zincon Method

1. General Discussion b. Interferences: The following ions interfere at concentra-

tions exceeding those listed:
a. Principle: Zinc forms a blue complex with 2-carboxy-2⬘-
hydroxy-5⬘-sulfoformazyl benzene (zincon) in a solution buff-
Ion mg/L Ion mg/L
ered to pH 9.0. Other heavy metals likewise form colored com-
2⫹ 3⫹
plexes with zincon. Cyanide is added to complex zinc and heavy Cd 1 Cr 10
metals. Cyclohexanone is added to free zinc selectively from its Al3⫹ 5 Ni2⫹ 20
cyanide complex so that it can be complexed with zincon to form Mn2⫹ 5 Cu2⫹ 30
Fe3⫹ 7 Co2⫹ 30
a blue color. Sodium ascorbate reduces manganese interference.
Fe2⫹ 9 CrO42⫺ 50
The developed color is stable except in the presence of copper
(see table below).
c. Minimum detectable concentration: 0.02 mg Zn/L.
ZINC (3500-Zn)/Zincon Method 3-107

2. Apparatus ascorbate, 5.0 mL buffer solution, 2.0 mL KCN solution, and 3.0
mL zincon solution. Pipet 20.0 mL of the solution into a clean
a. Colorimetric equipment: One of the following is required: 50-mL erlenmeyer flask. Reserve remaining solution to zero the
1) Spectrophotometer, for measurements at 620 nm, provid- instrument. Add 1.0 mL cyclohexanone to the erlenmeyer flask.
ing a light path of 1 cm or longer. Swirl for 10 s and note time. Transfer portions of both solutions
2) Filter photometer, providing a light path of 1 cm or longer to clean sample cells. Use solution without cyclohexanone to
and equipped with a red filter having maximum transmittance zero colorimeter. Read and record absorbance for solution with
near 620 nm. Deviation from Beer’s Law occurs when the filter cyclohexanone after 1 min. The calibration curve does not pass
band pass exceeds 20 nm. through zero because of the color enhancement effect of cyclo-
b. Graduated cylinders, 50-mL, with ground-glass stoppers, hexanone on zincon.
Class B or better. b. Treatment of samples: To determine readily acid-extract-
c. Erlenmeyer flasks, 50-mL. able total zinc, add 1 mL conc HCl to 50 mL sample and mix
d. Filtration apparatus: 0.45-␮m filters and filter holders. thoroughly. Filter and adjust to pH 7. To determine dissolved
zinc, filter sample through a 0.45-␮m membrane filter. Adjust to
3. Reagents pH 7 with 1N NaOH or 1N HCl if necessary after filtering.
c. Sample analysis: Cool samples to less than 30°C if neces-
a. Metal-free water: See Section 3111B.3c. Use water for sary. Analyze 20.0 mL of prepared sample as described in ¶ 4a
rinsing apparatus and preparing solutions and dilutions. above, beginning with “Add the following to each solution . . .”
b. Stock zinc solution: Dissolve 1000 mg (1.000 g) zinc metal If the zinc concentration exceeds 7 mg Zn/L prepare a sample
in 10 mL 1 ⫹ 1 HNO3. Dilute and boil to expel oxides of dilution and analyze a 20.0-mL portion.
nitrogen. Dilute to 1000 mL; 1.00 mL ⫽ 1.00 mg Zn.
c. Standard zinc solution: Dilute 10.00 mL stock zinc solution 5. Calculation
to 1000 mL; 1.00 mL ⫽ 10.00 ␮g Zn.
d. Sodium ascorbate, fine granular powder, USP. Read zinc concentration (in milligrams per liter) directly from
e. Potassium cyanide solution: Dissolve 1.00 g KCN in ap- the calibration curve.
proximately 50 mL water and dilute to 100 mL. CAUTION:
Potassium cyanide is a deadly poison. Avoid skin contact or 6. Precision and Bias
inhalation of vapors. Do not pipet by mouth or bring in contact
with acids. A synthetic sample containing 650 ␮g Zn/L, 500 ␮g Al/L, 50
f. Buffer solution, pH 9.0: Dissolve 8.4 g NaOH pellets in ␮g Cd/L, 110 ␮g Cr/L, 470 ␮g Cu/L, 300 ␮g Fe/L, 70 ␮g Pb/L,
about 500 mL water. Add 31.0 g H3BO3 and swirl or stir to 120 ␮g Mn/L, and 150 ␮g Ag/L in doubly demineralized water
dissolve. Dilute to 1000 mL with water and mix thoroughly. was analyzed in a single laboratory. A series of 10 replicates
g. Zincon reagent: Dissolve 100 mg zincon (2-carboxy-2⬘- gave a relative standard deviation of 0.96% and a relative error
hydroxy-5⬘-sulfoformazyl benzene) in 100 mL methanol. Be- of 0.15%. A wastewater sample from an industry in Standard
cause zincon dissolves slowly, stir and/or let stand overnight. Industrial Classification (SIC) No. 3333, primary smelting and
h. Cyclohexanone, purified. refining of zinc, was analyzed by 10 different persons. The mean
i. Hydrochloric acid, HCl, conc and 1N. zinc concentration was 3.36 mg Zn/L and the relative standard
j. Sodium hydroxide, NaOH, 6N and 1N. deviation was 1.7%. The relative error compared to results from
an atomic absorption analysis of the same sample was ⫺1.0%.
4. Procedure
7. Bibliography
a. Preparation of colorimetric standards: Accurately deliver
0, 0.5, 1.0, 3.0, 5.0, 10.0, and 14.0 mL standard zinc solution to PLATTE, J.A. & V.M. MARCY. 1959. Photometric determination of zinc
a series of 50-mL graduated mixing cylinders. Dilute each to with zincon. Anal. Chem. 31:1226.
RUSH, R.M. & J.H. YOE. 1954. Colorimetric determination of zinc and
20.0 mL to yield solutions containing 0, 0.25, 0.5, 1.5, 2.5, 5.0,
copper with 2-carboxy-2⬘-hydroxy-5⬘-sulfoformazyl-benzene.
and 7.0 mg Zn/L, respectively. (Lower-range standards may be Anal. Chem. 26:1345.
prepared to extend the quantitation range. Longer optical path MILLER, D.G. 1979. Colorimetric determination of zinc with zincon and
cells can be used. Verify linearity of response in this lower cyclohexanone. J. Water Pollut. Control Fed. 51:2402.
concentration range.) Add the following to each solution in PANDE, S.P. 1980. Study on the determination of zinc in drinking water.
sequence, mixing thoroughly after each addition: 0.5 g sodium J. IWWA XII (3):275.