Consequences of pH measurement errors

SUMMARY. 1. The pH range over which the effects of acidification on freshwater organisms become apparent may be quite narrow, in some cases less than half a pH unit. Therefore, accurate measurement is important, particularly in dilute surface waters near the biologically critical threshold of hydrogen ion activity.
2. A hypothetical example based on data from two species of fish illustrates the potential errors in predicting mean mortality when pH is measured by probes of varying accuracies, placing our results into an ecosystem management perspective. For a given error, there will be greater uncertainty in predicting mean mortality for species sensitive to increased hydrogen ion activity than for more tolerant species.
3. We review field pH measurement errors, and present unique laboratory (measurements at 1°C and under argon) and field comparisons of current instruments used for continuous, in situ pH monitoring, including the only instrument comparison in low conductivity waters during snow melt. Four operator or sampler-caused measurement errors and three electrode-caused pH measurement errors are illustrated with data from four common types of pH probes and meters.
4. Studies providing no confidence intervals for a set of pH measurements due to the lack of rigorous quality control and assurance procedures are of limited quantitative value to future investigators attempting to analyse temporal trends of surface water acidification. Management and policy decision attempts will remain seriously hampered until more interpretable results are routinely generated.