Nitrogen, Ammonia

DOC316.53.01235

Direct ISE Method1

Method 10001

0.1 to 10.0 mg/L NH3N

Ammonia ISE

Scope and application: For wastewater2.

1

Adapted from the Standard Methods for the Examination of Water and Wastewater, 20th Edition, Method 4500NH3E (with distillation).
Manual distillation is not necessary if comparability data on representative samples show that the distillation is not necessary. Manual
distillation is necessary to resolve controversies.
This method is USEPA Equivalent for wastewater and can be used for NPDES reporting.

Test preparation
Instrument-specific information
This procedure is applicable to the meters and probes that are shown in Table 1.
Procedures for other meters and probes can be different.
Table 1 Instrument-specific information
Meter

Probe

HQ30d portable single input, multi-parameter

IntelliCAL ISENH3181 ammonia ISE

HQ40d portable dual input, multi-parameter

HQ430d benchtop single input, multi-parameter
HQ440d benchtop dual input, multi-parameter
sensION+ MM340 lab dual input, pH/mV/ISE

sensION combination ammonia ISE (5192700)

sensION+ MM374 lab dual input, pH/mV/EC/ISE

sensION+ MM378 lab dual input, pH/ISE/EC/DO

Before starting
Refer to the meter documentation for meter settings and operation. Refer to probe documentation for probe preparation,
maintenance and storage information.
Prepare the probe before initial use. Refer to probe documentation.
When an IntelliCAL probe is connected to an HQd meter, the meter automatically identifies the measurement parameter
and is prepared for use.
Condition the probe before use. To condition the probe, put the probe in 100 mL of the lowest concentration standard
solution for a maximum of 1 hour.
Calibrate the probe before initial use. Refer to Calibration on page 3.
Stir the standards and samples at a slow and constant rate to prevent the formation of a vortex.
Air bubbles under the sensor tip can cause slow response or measurement errors. To remove the bubbles, carefully shake
the probe.
Small differences in concentration between samples can increase the stabilization time. Make sure to condition the probe
correctly. Try different stir rates to see if the stabilization time decreases.
During calibration, measure the standard solutions from lowest to highest concentration for best results.
Make sure that the calibration solutions and the samples are at the same temperature ( 2 C ( 3.6 F)) for best results.
Immediately before the test, adjust the sample pH to more than 11 with 10 N Sodium Hydroxide (or equivalent ISA), then
analyze the samples immediately for the best results. At high pH, ammonia solutions release ammonia into the atmosphere.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.

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.
This procedure is specified for the HQd meters. The sensION+ meters can be used, but the menus and navigation will be
different.

Items to collect
Description

Quantity

Ammonia ISA (TISAB)powder pillow or solution (1 pillow or 0.5 mL for each 25 mL of

solution)
Ammonia Nitrogen Standard Solution, 100 mg/L as NH3N

1
25 mL

Beaker, polypropylene, 50 mL, low form

3 or 4 (USEPA)

Stir bar, magnetic, 2.2 x 0.5 cm (7/8 x 3/16 in.)

3 or 4 (USEPA)

Stirrer, magnetic

Wash bottle with deionized water

Lint-free cloth

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

Sample collection

Collect samples in clean glass or plastic bottles with tight-fitting caps. Completely fill
the bottle and immediately tighten the cap.
Collect samples at less than 40 C (104 F). Ammonia is quickly released from
samples at more than 50 C (122 F). Use a cooling coil between the bottle and the
sampling point if necessary.
If chlorine is in the sample, immediately add 1 drop of 0.1 N Sodium Thiosulfate
Standard Solution for each 0.3 mg of chlorine in a 1-liter sample.
Analyze the samples as soon as possible for best results.
If prompt analysis is not possible, adjust the sample pH to between 2 and 1.5 with
concentrated sulfuric acid.
Keep the preserved samples at or below 6 C (43 F) for a maximum of 28 days.
Do not use mercuric chloride as a preservative because ammonia forms a complex
with mercuric ions.
Do not let the sample pH go to more than 10 before the test. At high pH, ammonia
solutions release ammonia into the atmosphere.
Correct the test result for the dilution caused by the volume additions.

Nitrogen, Ammonia, ISE Method (10.0 mg/L NH3-N)

Test procedure

1. Add 25 mL of sample to a
beaker.

2. Add the contents of one

Ammonia ISA Powder
Pillow.
Note: As an alternative, add
0.5 mL of Ammonia ISA
Solution.

3. Add a stir bar and put the

beaker on a magnetic
stirrer. Stir at a moderate
rate.

5. Put the probe in the

solution. Do not let the
probe touch the stir bar,
bottom or sides of the
container. Remove the air
bubbles from under the
probe tip.

6. Push Read. A progress

bar is shown. When the
measurement is stable, the
lock icon is shown.

7. Rinse the probe with

deionized water. Dry the
probe with a lint-free cloth.

2. Add the contents of one

Ammonia ISA Powder
Pillow.
Note: As an alternative, add
0.5 mL of Ammonia ISA
Solution.

3. Add a stir bar and put the

beaker on a magnetic
stirrer. Stir at a moderate
rate.

4. Rinse the probe with

deionized water. Dry the
probe with a lint-free cloth.

Calibration

1. Add 25 mL of the lowest

concentration standard
solution to a beaker.

Nitrogen, Ammonia, ISE Method (10.0 mg/L NH3-N)

4. Rinse the probe with

deionized water. Dry the
probe with a lint-free cloth.

5. Put the probe in the

solution. Do not let the
probe touch the stir bar,
bottom or sides of the
container. Remove the air
bubbles from under the
probe tip.

6. Push Calibrate. The

standard solution value is
shown.

7. Push Read. A progress

bar is shown. When the
measurement is stable, the
lock icon is shown.

9. Measure the remaining

standard solutions.

10. Push Done. A

calibration summary is
shown when the minimum
number of calibration
standards are measured.

11. Push Store to accept

the calibration.

8. Rinse the probe with

deionized water. Dry the
probe with a lint-free cloth.

Interferences
Distillation before ammonia analysis removes all inorganic interferences that form a
complex with ammonia.
Interfering substance

Interference level

Amines

Volatile low molecular weight gives a positive interference.

Mercury

Forms a metal complex with ammonia.

Silver

Forms a metal complex with ammonia.

Accuracy check
Slope method
Use the slope method to validate the electrode response.
1. Prepare two standard solutions that are one decade apart in concentration (e.g.,
1 mg/L and 10 mg/L or 10 mg/L and 100 mg/L). The minimum concentration is
0.2 mg/L.
2. Use the test procedure to measure the mV value of each standard solution.
3. Compare the mV value of each standard solution. The expected difference is 58 ( 3)
mV at 25 C (77 F).

Nitrogen, Ammonia, ISE Method (10.0 mg/L NH3-N)

Standard solution method

Use the standard solution method to validate the test procedure, the reagents (if
applicable) and the instrument.
Items to collect:

Standard solution within the test range

1. Use the test procedure to measure the concentration of the standard solution.
2. Compare the expected result to the actual result.
Standard additions method
Use the standard additions method to validate the test procedure, reagents and
instrument and to find if there is an interference in the sample.
Items to collect:

Nitrogen Ammonia Standard Solution, 100 mg/L

Graduated cylinder, 25 mL, polypropylene
TenSette pipet
Pipet tips

1.
2.
3.
4.
5.

Use a graduated cylinder to measure 25 mL of sample into a beaker.

Use the test procedure to measure the concentration of the sample.
Use the TenSette pipet to add 0.5 mL of the standard solution to the sample.
Measure the concentration of the spiked sample.
Compare the results before and after the standard solution addition. The
concentration should increase by 2 mg/L NH3N.

Temperature check
For probes that do not have a temperature sensor, measure the temperature of the
standard solutions and samples. Make sure that the calibration solutions and the samples
are at the same temperature ( 2 C ( 3.6 F)) for best results.

Clean the probe

Clean the probe when:

Drifting/inaccurate readings occur as a result of contamination on the sensing

element or incorrect storage conditions.
Slow response time occurs as a result of contamination on the sensing element.
The slope is out of range as a result of contamination on the sensing element.

For general contamination, complete the steps that follow.

1. Rinse the probe with deionized water. Blot dry with a lint-free cloth. Do not touch the
tip of the probe.
2. If harsh contaminants are attached to the probe, polish the probe tip with a soft cloth
or cotton swab to remove the contaminants.
3. Soak for 30 seconds in 25 mL of Ammonia Probe Storage Solution.

Summary of method
The ammonia electrode measures ammonia gas or ammonium ions in solutions. When a
strong base is added, ammonium ions in solutions become ammonia gas. The gas
diffuses through the membrane and causes a pH change in the thin layer of electrolyte.
The potential across the pH glass changes as a result of the pH change and the electrode
measures the change in potential. The measured pH change is proportional to the
ammonia concentration in the solution.

Nitrogen, Ammonia, ISE Method (10.0 mg/L NH3-N)

Consumables and replacement items

HQd meters and probes
Description

Unit

Item no.

HQ30d portable single input, multi-parameter meter

each

HQ30D53000000

HQ40d portable dual input, multi-parameter meter

each

HQ40D53000000

HQ430d benchtop single input, multi-parameter meter

each

HQ430D

HQ440d benchtop dual input, multi-parameter meter

each

HQ440D

IntelliCAL ISENH3181 digital ammonia ISE probe, 1 m cable

each

ISENH318101

IntelliCAL

each

ISENH318103

Description

Unit

Item no.

sensION+ MM340 lab dual input, pH/mV/ISE meter

each

LPV2200.97.0002

sensION+ MM374 lab dual input, pH/mV/EC/ISE meter

each

LPV4110.97.0002

sensION+ MM378 lab dual input, pH/ISE/EC/DO meter

each

LPV4130.97.0002

sensION+ Ammonia ISE probe

each

5192700

Unit

Item no.

Ammonia Ionic Strength Adjustor (ISA) Powder Pillows

100/pkg

4447169

Ammonia Ionic Strength Adjustor (ISA) Solution

500 mL

2824349

Nitrogen Ammonia Standard Solution, 100-mg/L as NH3N

500 mL

2406549

Nitrogen Ammonia Standard Solution, 1000-mg/L as NH3N

1L

2354153

Sodium Hydroxide Solution, 5 N

50 mL

245026

Sodium Hydroxide Standard Solution, 10 N

500 mL

2545049

Sodium Thiosulfate Standard Solution, 0.1 N

105 mL

32332

Sulfuric Acid, ACS

500 mL

97949

Description

Unit

Item no.

Beaker, polypropylene, 50-mL, low form

each

108041

Bottle, wash, 500-mL

each

62011

Graduated cylinder, polypropylene, 25-mL

each

108140

ISENH3181 digital ammonia ISE probe, 3 m cable

sensION+ meters and probes

Recommended reagents and standards

Description

Accessories

Pipet, TenSette , 0.11.0 mL

each

1970001

Pipet tips for TenSette Pipet, 0.11.0 mL

50/pkg

2185696

Probe clips, color-coded, for IntelliCAL probes

50/pkg

5818400

Probe holder, 3 probes, for sensION+ benchtop meters

each

LZW9321.99

Probe stand, universal

each

8508850

Stir bar, magnetic, 2.2 x 0.5 cm (7/8 x 3/16 in.)

each

4531500

Nitrogen, Ammonia, ISE Method (10.0 mg/L NH3-N)

Accessories (continued)
Description

Unit

Item no.

Stirrer, electromagnetic, 120 VAC, with electrode stand

each

4530001

Stirrer, electromagnetic, 230 VAC, with electrode stand

each

4530002

Nitrogen, Ammonia, ISE Method (10.0 mg/L NH3-N)

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING:

In the U.S.A. Call toll-free 800-227-4224
Outside the U.S.A. Contact the HACH office or distributor serving you.
On the Worldwide Web www.hach.com; E-mail techhelp@hach.com

Hach Company/Hach Lange GmbH, 19892015. All rights reserved.

HACH COMPANY
WORLD HEADQUARTERS
Telephone: (970) 669-3050
FAX: (970) 669-2932

03/2015, Edition 8