A detection decision threshold is a cutoff applied to an observed analytical response to decide whether there is evidence for an analyte contribution beyond background. A decision above the cutoff can be wrong even for an analytical blank: this is a type I error. Missing a genuine contribution is a type II error. The chosen rule and the measurement procedure determine those error probabilities.[ref]
For an original one-sided example, suppose blank responses have a known normal distribution . Set . Declaring detection when gives about a5percent type I error probability. A real sample whose mean is exactly has only a50percent chance of crossing that same detection decision threshold.
Under the additional assumption of unchanged standard deviation, a mean near gives about95percent probability of crossing it: the mean lies another units above . Thus an observed-response cutoff and a limit of detection giving a specified detection probability answer different questions. These numbers are a known-variance teaching model, not a universal laboratory convention. Estimating the background, changing the error criterion or allowing signal-dependent variance changes the calculation. The threshold must be tied to the complete procedure whose detection performance is claimed.[ref]
Limit of detection 2026-11-05
A limit of detection describes how small an analyte amount or concentration an analytical procedure can distinguish from its background with a stated degree of certainty. It depends on the procedure, background variation and chosen decision rule. An analytical blank supplies measurements without the intended analyte contribution; its response need not be exactly zero.[ref]
A simple model exposes the role of the decision rule. Suppose a single response satisfies , with known blank mean , positive response slope , analyte concentration and constant known standard deviation . Choose the detection decision threshold . Under the assumed normal distribution, a blank exceeds this threshold about5percent of the time. A sample whose mean merely equals exceeds it only half the time.
To obtain95percent probability of exceeding the same detection decision threshold, its mean must instead lie above it. The model therefore gives
For response units and response units per micromolar, . This is an original equal-variance, single-observation calculation, not a universal laboratory multiplier. Estimated blank uncertainty, unequal variance or a different error criterion changes the calculation. A detection claim also does not by itself establish a precise quantitative estimate of the analyte concentration.
Lloyd A. Currie 2026-11-05
Lloyd A. Currie prepared the 1995 IUPAC recommendations on evaluating analytical methods, including detection and quantification capabilities. A central contribution was to separate an observed-result decision from the capability of a measurement process. A detection decision threshold controls the chance of a false positive, while a limit of detection also depends on the chance of missing a real signal.[ref]
An original idealized example makes the distinction visible. Suppose the blank-corrected measurement has a normal distribution with standard deviation one. A threshold near gives a 5% type I error under a zero-mean blank model. A true mean near places that same threshold about standard deviations below the mean, giving about 95% detection probability, or 5% type II error.
The two signal levels answer different questions: whether one observed result crosses a decision boundary, and how strong a true signal must be for reliable detection under the assumed process. These numbers belong to the stated model; they are not universal detection limits for instruments.