DR/4000

PROCEDURE CADMIUM
Method 8017 Dithizone Method*
Powder Pillows (0 to 80.0 µg/L)
Scope and Application: For water and wastewater; digestion is required to determine total cadmium.
See Section 2 for digestion procedure. The estimated detection limit for program number 1350 is 1.3 µg/L Cd.

* Adapted from Standard Methods for the Examination of Water and Wastewater

HACH
PROGRAM

HACH PROGRAM:1350
1 3 5 0 Cadmium

ENTER

1. Press the soft key 2. The display will show: 3. Fill a 250-mL 4. Add the contents of
under HACH PROGRAM. HACH PROGRAM: 1350 graduated cylinder to the one Buffer Powder Pillow
Cadmium 250-mL mark with for heavy metals, citrate
Select the stored program sample. Pour the sample type. Stopper the funnel
number for cadmium (Cd) The wavelength (λ), into a 500-mL separatory and shake to dissolve.
by pressing 1350 with the 515 nm, is automatically funnel.
numeric keys. selected. Note: Clean all glassware
Press: ENTER Note: For proof of accuracy, with 6 N Hydrochloric Acid
use a 40 µg/L cadmium Solution and rinse with
Note: If samples cannot be
standard solution deionized water.
analyzed immediately, see
(preparation given in the Note: Cloudy and turbid
Sample Collection, Storage
Accuracy Check) in place of samples may require filtering
and Preservation following
the sample. before running the test.
these steps. Adjust the pH of
preserved samples before Note: For best results, Report results as µg/L
analysis. determine a reagent blank soluble cadmium.
for each new lot of reagent Use glass membrane type
Note: The Flow Cell and
as follows. Prepare a filter to avoid loss of
Sipper Modules cannot be
reagent blank by repeating cadmium by adsorption onto
used with this procedure.
steps 3 through 14, using the filter paper.
deionized water as the
sample. Zero the instrument
on chloroform by pressing
the soft key under ZERO.
Insert the reagent blank and
the blank value will be
displayed. Correct for the
reagent blank by pressing
the soft keys under OPTIONS,
(MORE), and then
BLANK:OFF. Enter the
reagent blank value and
press ENTER. Repeat for
each new lot of reagent.

CADMIUM
Cadmium_PP_Other_DTZ_Eng_4000.fm Page 1 of 8
CADMIUM, continued

START
TIMER

5. Add 30 mL of 6. Add 20 mL of 50% 7. Remove the stopper. 8. Add 30 mL of the

chloroform to a 50-mL Sodium Hydroxide Press the soft key under DithiVer solution to
mixing graduated Solution. Add a 0.1-g START TIMER. the 500-mL separatory
cylinder. Add the scoop of potassium A 1-minute reaction funnel. Stopper, invert,
contents of one DithiVer cyanide to the funnel. period will begin. and open stopcock to vent.
Metals Reagent Powder Stopper. Shake vigorously Close the stopcock and
Pillow. Stopper the for 15 seconds. shake funnel once or
cylinder. Invert several twice; vent again.
times to mix (this is the Warning: Cyanide is a
Press the soft key under
DithiVer solution). deadly poison. Use a fume
START TIMER. Close the
Note: Use adequate hood. Maintain cyanide
stopcock and shake the
ventilation for the extraction, solutions at pH 11 or
greater to prevent
funnel vigorously during
preferably a fume hood.
formation of cyanide gas. the 1 minute time period.
Note: The DithiVer powder
will not completely dissolve Note: Spilled reagent will
in the chloroform. For further affect test accuracy and is
notes see Dithiver Solution hazardous to skin and other
Preparation and Storage. materials. Please read the
MSDS before testing.

9. Press the soft key 10. Insert a cotton plug 11. Fill a dry 25-mL 12. Place the blank into
under START TIMER, the size of a pea into the sample cell with the cell holder. Close the
and allow the funnel to delivery tube of the funnel chloroform (the blank). light shield.
stand undisturbed until the and slowly drain the Stopper.
timer beeps. bottom (chloroform) layer
Note: The bottom into a dry 25-mL sample
(chloroform) layer will be cell (the prepared sample).
orange to pink if cadmium is Stopper.
present. Note: The cadmium-
dithizone complex is stable
for more than one hour if the
sample cell is kept tightly
capped and out of direct
sunlight.

CADMIUM
Page 2 of 8 Cadmium_PP_Other_DTZ_Eng_4000.fm
 CADMIUM, continued

ZERO

13. Press the soft key 14. Place the prepared

under ZERO. sample into the cell
The display will show: holder. Close the light
shield. Results in µg/L
0.0 µg/L Cd cadmium (or chosen units)
Note: If you are using a will be displayed.
reagent blank correction, Note: See Pollution
the display will show Prevention and Waste
the correction. Management following these
Note: For other steps for proper disposal of
concentration units, chloroform solutions.
press the soft key under
OPTIONS. Then press the
soft key under UNITS to scroll
through the available
options. Press ENTER to
return the read screen.

Interferences
The following do not interfere:
Aluminum Cobalt Manganese

Antimony Iron Nickel

Arsenic Lead Tin

Calcium Magnesium Zinc

Chromium

Table 1 Interfering Substances and Suggested Treatments

Interfering Substance Interference Levels and Treatments
Highly buffered samples or May exceed the buffering capacity of the reagents and require sample pretreatment;
Extreme sample pH see Section 1.3.1 pH Interference.
Bismuth Greater than 80 mg/L. See treatment below.
Copper Greater than 2 mg/L. See treatment below.
Mercury All levels. See treatment below.
Silver Greater than 2 mg/L. See treatment below.

CADMIUM
Cadmium_PP_Other_DTZ_Eng_4000.fm Page 3 of 8
CADMIUM, continued
Eliminate interference from the metals in the table by the following treatment,
beginning after Step 5.

a. Measure about 5-mL of the DithiVer solution into the separatory funnel.
Stopper the funnel, invert and open the stopcock to vent. Close the
stopcock and shake the solution vigorously for 15 seconds. Allow the
funnel to stand undisturbed until the layers separate (about 30 seconds).
A yellow, red, or bronze color in the bottom (chloroform) layer confirms
the presence of interfering metals. Draw off and collect the bottom
(chloroform) layer for proper disposal.
b. Repeat extraction with fresh 5 mL portions of the DithiVer solution
(discarding the bottom layer each time) until the bottom layer shows a
pure dark green color for three successive extracts. Extractions can be
repeated several times without appreciably affecting the amount of
cadmium in the sample.
c. Extract the solution with several 2- or 3-mL portions of pure chloroform to
remove any remaining DithiVer, collecting the bottom layer each time for
proper disposal.
d. Continue with Step 6 of the procedure.
e. In Step 8, substitute 28.5 mL of DithiVer solution for the 30 mL.
f. Continue with Step 9 of the procedure.

Sample Collection, Storage and Preservation

Collect samples in an acid-washed glass or plastic containers. Adjust the pH to 2
or less with nitric acid (about 2 mL per liter). Store preserved samples up to six
months at room temperature. Adjust the pH to 2.5 with 5.0 N sodium hydroxide
before analysis. Correct the test result for volume additions; see Section 1.2.2
Correcting for Volume Additions.

Dithiver Solution Preparation and Storage

Store DithiVer Powder Pillows away from light and heat. A convenient way to
prepare this solution is to add the contents of 16 DithiVer Metals Reagent Powder
Pillows to a 500-mL bottle of chloroform and invert several times until well mixed
(carrier powder may not dissolve completely). Store dithizone solution in an
amber glass bottle. This solution is stable for 24 hours.

Accuracy Check
Standard Additions Method

a. Leave the unspiked sample in the sample compartment. Verify that the
units displayed are in µg/L. Select standard additions mode by pressing the
soft keys under OPTIONS, (MORE) and then STD ADD.
b. Press ENTER to accept the default sample volume (mL), 250.
c. Press ENTER to accept the default standard concentration (µg/L), 25,000.
d. Press the soft key under ENTRY DONE.
e. Snap the neck off a Cadmium Voluette Ampule Standard, 25-mg/L Cd
(25,000-µg/L Cd).

CADMIUM
Page 4 of 8 Cadmium_PP_Other_DTZ_Eng_4000.fm
 CADMIUM, continued
f. Use the TenSette Pipet to add 0.1 mL, 0.2 mL and 0.3 mL of standard,
respectively to three 250-mL samples and mix each thoroughly.
g. Analyze each standard addition sample as described above. Accept the
standard additions reading by pressing the soft key under READ each time.
Each addition should reflect approximately 100% recovery.
h. After completing the sequence, the display will show the extrapolated
concentration value and the “best-fit” line through the standard additions
data points, accounting for matrix interferences.
i. See Section 1.4.1 Standard Additions for more information.

Standard Solution Method

Prepare a 5.0-mg/L cadmium standard solution by pipetting 5.00 mL of Cadmium
Standard Solution, 100-mg/L Cd, into a 100-mL volumetric flask. Dilute to the
mark with deionized water. Prepare this solution daily. Pipet 2.00 mL of the
5.0-mg/L Cadmium Standard Solution into 248 mL of deionized water in a
500-mL separatory funnel. This is a 40-µg/L cadmium solution. Perform the
cadmium test on this solution beginning with Step 4 of the procedure.

Method Performance
Precision
Standard: 40.0 µg/L Cd

Program 95% Confidence Limits

1350 39.3–40.7 µg/L Cd

For more information on determining precision data and method detection limits,
refer to Section 1.5.

Estimated Detection Limit

Program EDL
1350 1.3 µg/L Cd

For more information on derivation and use of Hach’s estimated detection limit,
see Section 1.5.2. To determine a method detection limit (MDL) as defined by the
40 CFR part 136, Appendix B, see Section 1.5.1.

Sensitivity
Program Number: 1350

Portion of Curve: ∆Abs ∆Concentration

Entire Range 0.010 0.73 µg/L

See Section 1.5.3 Sensitivity Explained for more information.

Calibration Standard Preparation

To perform a cadmium calibration using the dithizone method, prepare a 1,000-µg/L
cadmium stock solution by pipetting 10.00 mL of a 100-mg/L Cadmium Standard
Solution (Cat. No. 14024-42) into a 1000-mL volumetric flask using Class A
glassware. Dilute to the mark with deionized water and mix thoroughly.

CADMIUM
Cadmium_PP_Other_DTZ_Eng_4000.fm Page 5 of 8
CADMIUM, continued
Prepare calibration standard containing 12.00, 36.00, 64.00 and 80.00 µg/L Cd
as follows:

a. Into four different 250-mL volumetric flasks, pipet 3.00, 9.00, 16.00 and
20.00 mL of the 1,000-µg/L Cd stock solution using Class A glassware.
b. Dilute to the mark with deionized water and mix thoroughly.
c. Using the dithizone method and the calibration procedure described in
the User-Entered Programs section of the DR/4000 Spectrophotometer
Instrument Manual, generate a calibration curve from the standards
prepared above.

Summary of Method
The dithizone method is designed for the determination of cadmium in water and
wastewater. The DithiVer Metals Reagent is a stable powder form of dithizone.
Cadmium ions in basic solution react with dithizone to form a pink to red
cadmium-dithizonate complex, which is extracted with chloroform.

Safety
Good safety habits and laboratory techniques should be used throughout the
procedure. Consult the Material Safety Data Sheet for information specific to
the reagents used. For additional information, refer to Section 3.

Pollution Prevention and Waste Management

Both chloroform (D022) and cyanide (D003) solutions are regulated as hazardous
wastes by the Federal RCRA. Do not pour these solutions down the drain.
Chloroform solutions and the cotton plug used in the delivery tube of the
separatory funnel should be collected for disposal with laboratory solvent waste.
Collect the cyanide solution as a reactive waste. Be sure that cyanide solutions
are stored in a caustic solution with a pH >11 to prevent potential release of
hydrogen cyanide gas. See Section 3 for more information on proper disposal
of these materials.

CADMIUM
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 CADMIUM, continued

REQUIRED REAGENTS AND STANDARDS

Cat. No.
Cadmium Reagent Set (100 Tests) ..........................................................................................................22422-00
Includes: (1) 14202-99, (1) 14458-17, (1) 12616-99, (1) 767-14, (4) 2180-49, (1) 2572-01
Quantity Required
Description per test Unit Cat. No.
Buffer Powder Pillows, citrate ....................................................... 1 pillow............ 100/pkg.................14202-99
Chloroform, ACS ............................................................................ 30 mL .....................4 L.................14458-17
DithiVer Metals Reagent Powder Pillows ...................................... 1 pillow ............ 100/pkg.................12616-99
Potassium Cyanide ............................................................................0.1 g .................. 125 g.....................767-14
Sodium Hydroxide Solution, 50% .................................................. 20 mL ..............500 mL...................2180-49
Cotton Balls, absorbent ........................................................................1 ................. 100/pkg...................2572-01

REQUIRED EQUIPMENT AND SUPPLIES

Clippers, for opening powder pillows ..................................................1 ....................... each.....................968-00
Cylinder, graduated, 25-mL .................................................................1 ....................... each.....................508-40
Cylinder, graduated, 250-mL ...............................................................1 ....................... each.....................508-46
Cylinder, graduated, mixing, 50-mL ....................................................1 ....................... each...................1896-41
Sample Cells, matched pair, 1-inch, glass, with stopper......................2 ........................ pair.................26126-02
DR/4000 1-Inch Cell Adapter ..............................................................1 ....................... each.................48190-00
Funnel, separatory, 500-mL .................................................................1 ....................... each.................... 520-49
Spoon, measuring, 0.1-g.......................................................................1 ....................... each.....................511-00
Support Ring, 4"...................................................................................1 ....................... each.....................580-01
Support Ring Stand, 5" x 8" base .........................................................1 ....................... each.....................563-00

OPTIONAL REAGENTS AND STANDARDS

Cadmium Standard Solution, 100-mg/L Cd..............................................................100 mL.................14024-42
Cadmium Standard Solution, 10-mL Voluette Ampule, 25-mg/L Cd........................ 16/pkg.................14261-10
Hydrochloric Acid Solution, 6.0 N ...........................................................................500 mL.....................884-49
Sodium Hydroxide Standard Solution, 5.0 N..................................................100 mL MDB...................2450-32
Sodium Hydroxide Standard Solution, 5.0 N.................................................. 59 mL SCDB...................2450-26
Water, deionized ......................................................................................................... 4 liters.....................272-56
Chloroform, ACS ......................................................................................................500 mL.................14458-49

CADMIUM
Cadmium_PP_Other_DTZ_Eng_4000.fm Page 7 of 8
CADMIUM, continued

OPTIONAL EQUIPMENT AND SUPPLIES

Description Unit Cat. No.
Ampule Breaker Kit ....................................................................................................... each.................21968-00
Cylinder, graduated, 5-mL ............................................................................................. each.....................508-37
DR/4000 Carousel Module Kit ...................................................................................... each.................48090-02
Filter Discs, glass, 47 mm ........................................................................................ 100/pkg...................2530-00
Filter Holder, glass, for 47-mm filter ............................................................................. each...................2340-00
Flask, Erlenmeyer, 500-mL............................................................................................ each .....................505-49
Flask, filtering, 500-mL ................................................................................................. each.....................546-49
Flask, volumetric, Class A, 100-mL .............................................................................. each.................14574-42
Flask, volumetric, Class A, 250-mL .............................................................................. each.................14574-46
Flask, volumetric, Class A, 1000-mL, with glass stopper.............................................. each.................14574-53
Hot Plate, 3½-in. diameter, 120 VAC, 50/60 Hz ............................................................ each .................12067-01
Hot Plate, 3½-in. diameter, 240 VAC, 50/60 Hz, variable control ................................. each.................12067-02
pH Paper, pH 1.0 to 11.0 ...................................................................................... 5 rolls/pkg.....................391-33
pH Meter, sension™1, portable.................................................................................... each.................51700-00
Pipet, serological, 2-mL ................................................................................................. each.....................532-36
Pipet, TenSette, 0.1 to 1.0 mL ........................................................................................ each.................19700-01
Pipet Tips, for 19700-01 TenSette Pipet .................................................................... 50/pkg.................21856-96
Pipet, volumetric, 2.00-mL, Class A ............................................................................. each.................14515-36
Pipet, volumetric, 3.00-mL, Class A .............................................................................. each.................14515-03
Pipet, volumetric, 6.00-mL, Class A .............................................................................. each.................14515-06
Pipet, volumetric, 8.00-mL, Class A .............................................................................. each.................14515-08
Pipet, volumetric, 9.00-mL, Class A .............................................................................. each.................14515-09
Pipet, volumetric, 10.00-mL, Class A ............................................................................ each.................14515-38
Pipet, volumetric, 20.00-mL, Class A ............................................................................ each.................14515-20
Pipet Filler, safety bulb................................................................................................... each.................14651-00
Tongs, crucible, 9-inch ................................................................................................... each.....................569-00

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY

In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – [email protected] FAX: (970) 669-2932

© Hach Company, 1997-2003. All rights reserved. Printed in the U.S.A. 6/03 11ed
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