Zinc DOC316.53.

01145

USEPA1 Zincon Method2 Method 8009

0.01 to 3.00 mg/L Zn Powder Pillows
Scope and application: For water and wastewater. Digestion is required for a total zinc analysis.
1 USEPA approved for wastewater analyses 3500 Zn B: Federal Register, 45(105) 36166 (May 29, 1980).
2 Adapted from Standard Methods for the Examination of Water and Wastewater.

Test preparation

Instrument-specific information
Table 1 shows all of the instruments that have the program for this test. The table also
shows sample cell and orientation requirements for reagent addition tests, such as
powder pillow or bulk reagent tests.
To use the table, select an instrument, then read across to find the applicable information
for this test.
Table 1 Instrument-specific information
Instrument Sample cell orientation Sample cell
DR 6000 The fill line is to the right. 2495402
DR 3800
DR 2800
DR 2700
DR 1900
DR 5000 The fill line is toward the user.
DR 3900
DR 900 The orientation mark is toward the user. 2401906

Before starting
Install the instrument cap on the DR 900 cell holder before ZERO or READ is pushed.
Clean all glassware with 6.0 N (1:1) hydrochloric acid, then fully rinse with deionized water to remove contaminants.
Use only glass-stoppered mixing cylinders in this procedure.
Make sure that the dropper that is used in this procedure is plastic. Droppers that have rubber bulbs can contaminate the
reagent.
The reagents that are used in this test contain potassium cyanide. Keep cyanide solutions at pH > 11 to prevent
exposure to hydrogen cyanide gas. Collect the reacted samples for proper disposal.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Do not use the Pour-Thru Cell or sipper module (for applicable instruments) with this test.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

1
Items to collect
Description Quantity

Cyclohexanone 0.5 mL
ZincoVer® 5 Reagent Powder Pillow, 20-mL 1
Mixing cylinder, graduated, 25-mL, glass stopper 1
Sample cells (For information about sample cells, adapters or light shields, refer to Instrument-
2
specific information on page 1.)

Refer to Consumables and replacement items on page 6 for order information.

Sample collection and storage

• Collect samples in clean glass or plastic bottles that have been cleaned with 6 N (1:1)
hydrochloric acid and rinsed with deionized water.
• To preserve samples for later analysis, adjust the sample pH to less than 2 with
concentrated nitric acid (about 2 mL per liter). No acid addition is necessary if the
sample is tested immediately.
• Keep the preserved samples at room temperature for a maximum of 6 months.
• Before analysis, adjust the pH to 4–5 with 5 N sodium hydroxide solution. Do not
exceed pH 5 as zinc can precipitate. Do not add the reagent to samples with pH less
than 4 because there is cyanide in the reagent.
• Correct the test result for the dilution caused by the volume additions.

Powder pillow procedure

Start

1. Start program 780 Zinc. 2. Fill a 25-mL graduated 3. Add the contents of one 4. Shake the cylinder
For information about mixing cylinder with 20 mL ZincoVer 5 Reagent Powder vigorously to dissolve the
sample cells, adapters or of sample. Pillow to the mixing cylinder. powder completely.
light shields, refer to Close the cylinder. Inconsistent readings can
Instrument-specific result if all the particles are
information on page 1. not dissolved.
Note: Although the program The sample should be
name can be different orange. If the sample is
between instruments, the brown or blue, the zinc
program number does not concentration is too high or
change. an interfering metal is
present. Dilute the sample
and repeat the test.

2 Zinc, Zincon Method (3.00 mg/L)

5. Blank preparation: Pour 6. Prepared sample: Use a 7. Start the instrument 8. During the reaction
10 mL of the solution into a plastic dropper to add timer. A 30-second reaction period, close the mixing
sample cell. 0.5 mL of cyclohexanone to time starts. cylinder and vigorously
the solution in the mixing shake the prepared sample.
cylinder. The sample becomes
reddish-orange, brown or
blue, depending on the zinc
concentration.

9. Start the instrument 10. Pour the prepared 11. When the timer expires, 12. Insert the blank into the
timer. A 3-minute reaction sample solution from the clean the blank sample cell. cell holder.
time starts. mixing cylinder into a
During the reaction period, second sample cell.
complete the next step.

Zero Read

13. Push ZERO. The 14. Clean the prepared 15. Insert the prepared 16. Push READ. Results
display shows 0.00 mg/L Zn. sample cell. sample into the cell holder. show in mg/L Zn.

Interferences
Interfering substance Interference level
Aluminum More than 6 mg/L
Cadmium More than 0.5 mg/L
Copper More than 5 mg/L
Iron (ferric) More than 7 mg/L
Manganese More than 5 mg/L

Zinc, Zincon Method (3.00 mg/L) 3

Interfering substance Interference level
Nickel More than 5 mg/L
Organic Material Large amounts may interfere. Pretreat the sample with a digestion.
Highly buffered samples or Can prevent the correct pH adjustment of the sample by the reagents. Sample pre-
extreme sample pH treatment may be necessary. Adjust the pH to 4–5.
Amino-tri(methylene phosphonic Samples that contain AMP cause a negative interference. Digest the sample to remove
acid) (AMP) this interference (use the total phosphorus hot plate digestion, Method 8190).
Note: Be sure to adjust the pH of the sample after the digestion to pH 4–5 with sodium hydroxide
before the zinc analysis.

Digestion
For total zinc determinations, the sample must be digested with heat and acid to make
sure that all forms of the metal are measured. The steps that follow can be used for a
mild digestion.
Note: The following procedure is the USEPA mild digestion procedure. Refer to the Water Analysis
Guide for more digestion procedures.

1. Add concentrated nitric acid to the sample with a glass serological pipet and pipet
filler:
• If the sample was acidified for preservation, add 3 mL of nitric acid to 1 liter of the
preserved sample.
• If the sample was not acidified for preservation, add 5 mL of nitric acid to 1 liter of
sample.
2. Transfer 100 mL of acidified sample to a 250-mL Erlenmeyer flask.
3. Add 5 mL of 1:1 hydrochloric acid.
4. Put the sample on a hot plate at 95 °C (203 °F) until 15–20 mL of the sample
remains. Make sure that the sample does not boil.
5. Put the cooled sample through a 0.45-µm filter to remove any insoluble material.
6. Adjust the pH of the digested sample to pH 4–5 with 5.0 N sodium hydroxide. Do not
exceed pH 5 as zinc may precipitate.
7. Quantitatively transfer the sample to a 100-mL volumetric flask and dilute to the mark
with deionized water.

Accuracy check
Standard additions method (sample spike)
Use the standard additions method (for applicable instruments) to validate the test
procedure, reagents and instrument and to find if there is an interference in the sample.
Items to collect:
• 25-mg/L Zinc Voluette® Ampule Standard Solution
• Ampule breaker
• Pipet, TenSette®, 0.1–1.0 mL and tips
• Mixing cylinders, 25-mL (3)

1. Use the test procedure to measure the concentration of the sample, then keep the
(unspiked) sample in the instrument.
2. Go to the Standard Additions option in the instrument menu.
3. Select the values for standard concentration, sample volume and spike volumes.
4. Open the standard solution.
5. Prepare three spiked samples: use the TenSette pipet to add 0.1 mL, 0.2 mL and
0.3 mL of the standard solution, respectively, to three 20-mL portions of fresh sample.
Mix well.

4 Zinc, Zincon Method (3.00 mg/L)

 6. Use the test procedure to measure the concentration of each of the spiked samples.
Start with the smallest sample spike. Measure each of the spiked samples in the
instrument.
7. Select Graph to compare the expected results to the actual results.
Note: If the actual results are significantly different from the expected results, make sure that
the sample volumes and sample spikes are measured accurately. The sample volumes and
sample spikes that are used should agree with the selections in the standard additions menu. If
the results are not within acceptable limits, the sample may contain an interference.

Standard solution method

Use the standard solution method to validate the test procedure, the reagents and the
instrument.
Items to collect:
• 100-mg/L zinc standard solution
• 1-L volumetric flask, Class A
• 10-mL volumetric pipet, Class A and pipet filler safety bulb
• Deionized water

1. Prepare a 1.00-mg/L zinc standard solution as follows:

a. Use a pipet to add 10.00 mL of 100-mg/L zinc standard solution into the
volumetric flask.
b. Dilute to the mark with deionized water. Mix well. Prepare this solution daily.
2. Use the test procedure to measure the concentration of the prepared standard
solution.
3. Compare the expected result to the actual result.
Note: The factory calibration can be adjusted slightly with the standard adjust option so that the
instrument shows the expected value of the standard solution. The adjusted calibration is then
used for all test results. This adjustment can increase the test accuracy when there are slight
variations in the reagents or instruments.

Method performance
The method performance data that follows was derived from laboratory tests that were
measured on a spectrophotometer during ideal test conditions. Users can get different
results under different test conditions.
Program Standard Precision (95% confidence interval) Sensitivity
Concentration change per 0.010 Abs change
780 1.00 mg/L Zn 0.97–1.03 mg/L Zn 0.013 mg/L Zn

Summary of method
Zinc and other metals in the sample are complexed with cyanide. Adding cyclohexanone
causes a selective release of zinc. The zinc reacts with 2-carboxy-2'-hydroxy-5'-
sulfoformazyl benzene (zincon) indicator to form a blue-colored species. The blue color is
masked by the brown color from the excess indicator. The intensity of the blue color is
proportional to the amount of zinc present. The measurement wavelength is 620 nm for
spectrophotometers or 610 nm for colorimeters.
Pollution prevention and waste management
Reacted samples contain potassium cyanide and must be disposed of as a hazardous
waste. Dispose of reacted solutions according to local, state and federal regulations.

Zinc, Zincon Method (3.00 mg/L) 5

Consumables and replacement items
Required reagents

Description Quantity/test Unit Item no.

Zinc Reagent Set, 20-mL sample size, includes: — 100 tests 2429300
Cyclohexanone 0.5 mL 100 mL MDB 1403332
®
ZincoVer 5 Reagent Powder Pillow, 20-mL 1 100/pkg 2106669

Required apparatus

Description Quantity/test Unit Item no.

Mixing cylinder, graduated, 25-mL with stopper 1 each 2088640

Recommended standards

Description Unit Item no.

Water, deionized 4L 27256

Zinc Standard Solution, 100-mg/L 100 mL 237842
®
Zinc Standard Solution, 10-mg/L Voluette Ampule, 25-mL as Zn 16/pkg 1424610
Zinc Standard Solution, 1000-mg/L 100 mL 1417742

Optional reagents and apparatus

Description Unit Item no.

Flask, Erlenmeyer, 250-mL each 50546

Hot plate, 4-inch round, 120 V each 1206701
Hydrochloric Acid Solution, 6.0 N (1:1) 500 mL 88449
Nitric Acid, concentrated 500 mL 15249
®
Pipet, TenSette , 0.1–1.0 mL each 1970001
®
Pipet tips for TenSette Pipet, 0.1–1.0 mL 50/pkg 2185696
®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
Pipet, volumetric, Class A, 10-mL each 1451538
Pipet filler, safety bulb each 1465100
Flask, volumetric, Class A, 1000-mL glass each 1457453

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© Hach Company/Hach Lange GmbH, 1989–2014. All rights reserved. 01/2014, Edition 8