Method 8143

For water, wastewater and seawater

COPPER (0 to 210.0 g/L)

Porphyrin Method*

1. Enter the stored

2. Press: 22 ENTER

program number for

copper (Cu), porphyrin
method.

with 10 mL of sample.
The display will show
g/L, Cu and the ZERO Note: Wash all glassware
with detergent. Rinse with
icon.

Press: PRGM

Note: Total copper

determination needs a
prior digestion; use either
the Digesdahl or vigorous
digestion (Section 2).

The display will show:

PRGM ?

5. Add the contents of

one Porphyrin 1 Reagent
Powder Pillow to each
sample cell. Swirl to
dissolve the powder.

3. Fill two sample cells 4. Add the contents of

one Copper Masking
Reagent Powder Pillow
to one of the sample
tap water. Rinse again with cells (the blank). Swirl
Nitric Acid Solution, 1:1.
to dissolve.
Rinse a third time with
copper-free,
deionized water.

6. Add the contents of

7. Press:
one Porphyrin 2 Reagent
TIMER ENTER
Powder Pillow to each
A three-minute reaction
sample cell. Swirl to
period will begin.
dissolve the powder.

Note: The yellow color will

turn blue momentarily. If
any copper is present, the
yellow color will return.

* Adapted from Ishii and Koh, Bunseki Kagaku, 28 473 (1979)

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Note: The other sample

cell is the prepared sample.

8. After the timer beeps,

place the blank into the
cell holder. Tightly
cover the sample cell
with the instrument cap.

COPPER, continued

10. Place the prepared

The cursor will move to sample into the cell
holder. Tightly cover the
the right, then the
sample cell with the
display will show:
instrument cap.
0.0 g/L Cu

9. Press: ZERO

Note: If samples with high

levels of metal are
analyzed, a slight metallic
deposit or yellow buildup
may appear on the sample
cell wall. Remove by
rinsing with nitric acid.
Dilute a fresh sample and
repeat the test. Multiply the
result by the dilution
factor; see Section 1.

11. Press: READ

The cursor will move to

the right, then the result
in g/L copper (Cu) will
be displayed.
Note: Standard Adjust may
be performed using a
prepared standard (see
Standard Adjust in
Section 1).

Sampling and Storage

Collect samples in acid-washed plastic bottles. To preserve,
adjust the pH to 2 or less with nitric acid (about 5 mL per liter).
Store preserved samples up to six months at room temperature.
Before testing, adjust the pH of the sample to between 2 and 6. If
the sample is too acidic, adjust the pH with 5.0 N Sodium
Hydroxide Standard Solution. Correct test results for volume
additions; see Correction for Volume Additions in Section 1 for
more information.

188

COPPER, continued
Accuracy Check
Standard Additions Method
a) Fill six (3 pairs) 25-mL graduated mixing cylinders with
25 mL of sample. Properly mark each pair of cylinders as
sample
and blank.
b) Using a TenSette Pipet, add 0.1 mL of Copper Standard
Solution, 10.0 mg/L Cu, to two of the cylinders. Add 0.2
mL of standard to two more of the cylinders. Add 0.3 mL
of standard to the other two cylinders, making a total of
six samples (2 for each volume
of standard).
c) Analyze the samples as described above. The copper
concentration reading should increase by 40 g/L for
each 0.1 mL of standard added.
d) If these increases do not occur, see Standard Additions in
Section 1 for more information.
Standard Solution Method
To assure the accuracy of the test, prepare a 100 g/L copper
standard:
a) Pipet 1.00 mL of Copper Standard Solution, 10.0 mg/L
Cu, into a 100-mL volumetric flask.
b) Dilute to volume with copper-free, reagent-grade water.
c) Use this standard in place of the sample in the procedure.
The reading should be 100 g/L Cu.
d) Prepare this solution daily.
Method Performance
Precision
In a single laboratory, using a standard solution of 100 g/L
copper and two representative lots of reagent with the instrument,
a single operator obtained a standard deviation of 3.4 g/L
copper.
Estimated Detection Limit
The estimated detection limit for program 22 is 5.4 g/L Cu. For
more information on the estimated detection limit, see Section 1.
189

COPPER, continued
Interferences
The following may interfere when present in concentrations
exceeding those listed below:
Substance

Concentration

Substance

Concentration

Aluminum

60 mg/L

Magnesium

10,000 mg/L

Cadmium

10 mg/L

Manganese

140 mg/L

Calcium

15,000 mg/L

Mercury

3 mg/L

Chloride

90,000 mg/L

Molybdenum

11 mg/L

Chromium (Cr6+)

110 mg/L

Nickel

60 mg/L

Cobalt

100 mg/L

Potassium

60,000 mg/L

Fluoride

30,000 mg/L

Sodium

90,000 mg/L

Iron (Fe2+)

6 mg/L

Zinc

9 mg/L

Lead

3 mg/L

Chelating agents, such as EDTA, interfere at all levels unless

either the Digesdahl or vigorous digestion (Section 2) is
performed.
Highly buffered samples or extreme sample pH may exceed the
buffering capacity of the reagents and require sample
pretreatment: see pH Interferences in Section 1.
Summary of Method
The porphyrin method is very sensitive to trace amounts of free
copper. Due to the sensitivity of the method, a masking agent is
used to prepare a blank for each sample. The method is free
from most interferences and does not require any sample
extraction or preconcentration. Interferences from other metals
are eliminated by the copper masking reagent. The porphyrin
indicator forms an intense, yellow-colored complex proportional
to any free copper present in the sample. Total copper may be
determined if a digestion is performed prior to analysis.

190

COPPER, continued
REQUIRED REAGENTS
Cat. No.

Copper Reagent Set, 10-mL samples (100 tests) ..........................................................26033-00

Includes: (1) 26034-49, (2) 26035-49, (2) 26036-49
Description

Quantity Required
Per Test

Unit

Cat. No.

Copper Masking Reagent Powder Pillows.............. 1 pillow................100/pkg ..........26034-49

Porphyrin 1 Reagent Powder Pillows..................... 2 pillows...............100/pkg ..........26035-49
Porphyrin 2 Reagent Powder Pillows..................... 2 pillows...............100/pkg ..........26036-49
REQUIRED APPARATUS
Sample Cell, 10-20-25 mL, w/ caps..............................2 .........................6/pkg ..........24019-06
OPTIONAL REAGENTS
Copper Standard Solution, 10 mg/L Cu ................................................ 100 mL ..............128-42
Hydrochloric Acid Solution, 1:1 (6 N).................................................. 500 mL ..............884-49
Nitric Acid, ACS ................................................................................... 500 mL ..............152-49
Nitric Acid Solution, 1:1 ....................................................................... 500 mL ............2540-49
Sodium Hydroxide Standard Solution, 5 N.................................................. 1 L ............2450-53
Water, deionized ........................................................................................... 4 L ..............272-56
OPTIONAL APPARATUS
Beaker, 100 mL ...........................................................................................each ...........500-42H
Cylinder, mixing, graduated, 25 mL ...........................................................each ..........20886-40
Flask, volumetric, Class A, 100 mL............................................................each ..........14574-42
Hot Plate, 7 x 7 inches, 120 V.....................................................................each ..........23441-00
Hot Plate, 7 x 7 inches, 240 V.....................................................................each ..........23441-02
pH Paper, 1 to 11 pH units ................................................................5 rolls/pkg ..............391-33
pH Meter, sension1, portable, with electrode...........................................each ..........51700-10
Pipet, Mohr, 5 mL .......................................................................................each ..........20934-37
Pipet, TenSette, 0.1 to 1.0 mL .....................................................................each ..........19700-01
Pipet Tips, for 19700-01..........................................................................50/pkg ..........21856-96
Pipet Tips, for 19700-01......................................................................1000/pkg ..........21856-28
Pipet, volumetric, 1.0 mL, Class A .............................................................each ..........14515-35
Pipet Filler, safety bulb ...............................................................................each ..........14651-00
Watch Glass, Pyrex, 100 mL.....................................................................each ..............578-70
For Technical Assistance, Price and Ordering
In the U.S.A.Call 800-227-4224
Outside the U.S.A.Contact the Hach office or distributor serving you.

191