Uncertainty Budgets and Calculations for: Ammonia

Step 1: Specify Measurand

Clear statement of what is being measured, including relationship between the measurand and the input quantities
(eg measured quantities, constant, calibration standard values, etc) upon which it depends. Where possible include
corrections for known systematic effects. The specification information should be given in the relevant Standard
Operating Procedure or other method.

Ammonia (in sewage, effluents and raw waters) reacts with hypochlorite and salicylate ions in
the presence of sodium nitroprusside. A coloured compound is formed and its concentration
is determined spectrophotometrically at 660nm, by comparison with a calibration curve.

Step 2: Identify Uncertainty Sources

List the possible sources of uncertainty. This will include sources that contribute to the uncertainty on the
parameters specified in step 1, but may include other sources and must include sources arising from chemical
assumptions.

Ishikawa (fishbone diagram):

Spectrophotometer Solution Prep Reproducibility

Weight Interferences
Chemicals
Glassware
Accuracy Purity
Tolerances

Wavelength

Repeatability
Ammonia

Over-range Blanks

Balances
Completed ? Too high?

Curve

Linearity

Chemical Reaction Calibration

Uncertainty Components: Significant? Covered in NS30/CRM/etc?

Wavelength No Set for each

analysis, curve
takes account of
this

Solution prep Yes Covered in NS30

Reproducibility Yes Covered in NS30

& bias testing;
interferences low

Reaction Yes Covered by NS30

Calibration Yes All factors covered

by NS30 and the
calibration curve
for each batch of
analyses.
Step 3: Quantify Uncertainty Components
Measure or estimate the size of the uncertainty component associated with each potential source of uncertainty
identified. It is often possible to estimate or determine a single contribution to uncertainty associated with a number
of separate sources. It is also important to consider whether available data accounts sufficiently for all sources of
uncertainty, and plan additional experiments and studies carefully to ensure that all sources of uncertainty are
adequately accounted for.

From NS30 testing (11 batches), total standard deviation for spiked effluent (the highest value)
is 0.00729mg/l

From Aquacheck (24 results), the uncertainty (i.e. standard deviation) for all matrices (clean,
waste and trade) is -0.02337mg/l

All other uncertainties are covered within these two values.

Step 4: Calculate Combined Uncertainty
The information obtained in step 3 will consist of a number of quantifies contributions to overall uncertainty, whether
associated with individual sources or with the combined effects of several sources. The contributions have to be
expresses as standard deviations, and combined according to the appropriate rules, to give a combined uncertainty.
The appropriate coverage factor should be applies to give an expanded uncertainty.

Combined Uncertainty = Ö(0.007292 + 0.023372)

= 0.02448

Expanded Uncertainty (k =2 because there are more than 6 degrees of freedom)

= 0.02448 x 2

= 0.04896

Result can be reported as x + (0.049*x)