Determine the detection limit based on using a calibration line (or curve) and inverse regression.
detectionLimitCalibrate(object, coverage = 0.99, simultaneous = TRUE)
an object of class
optional numeric scalar between 0 and 1 indicating the confidence level associated with
the prediction intervals used in determining the detection limit.
The default value is
optional logical scalar indicating whether to base the prediction intervals on
simultaneous or non-simultaneous prediction limits. The default value is
The idea of a decision limit and detection limit is directly related to calibration and can be framed in terms of a hypothesis test, as shown in the table below. The null hypothesis is that the chemical is not present in the physical sample, i.e., H_0: C = 0, where C denotes the concentration.
|Your Decision||H_0 True (C = 0)||H_0 False (C > 0)|
|Reject H_0||Type I Error|
|(Declare Chemical Present)||(Probability = α)|
|Do Not Reject H_0||Type II Error|
|(Declare Chemical Absent)||(Probability = β)|
Ideally, you would like to minimize both the Type I and Type II error rates. Just as we use critical values to compare against the test statistic for a hypothesis test, we need to use a critical signal level S_D called the decision limit to decide whether the chemical is present or absent. If the signal is less than or equal to S_D we will declare the chemical is absent, and if the signal is greater than S_D we will declare the chemical is present.
First, suppose no chemical is present (i.e., the null hypothesis is true). If we want to guard against the mistake of declaring that the chemical is present when in fact it is absent (Type I error), then we should choose S_D so that the probability of this happening is some small value α. Thus, the value of S_D depends on what we want to use for α (the Type I error rate), and the true (but unknown) value of σ (the standard deviation of the errors assuming a constant standard deviation) (Massart et al., 1988, p. 111).
When the true concentration is 0, the decision limit is the (1-α)100th percentile of the distribution of the signal S. Note that the decision limit is on the scale of and in units of the signal S.
Now suppose that in fact the chemical is present in some concentration C (i.e., the null hypothesis is false). If we want to guard against the mistake of declaring that the chemical is absent when in fact it is present (Type II error), then we need to determine a minimal concentration C_DL called the detection limit (DL) that we know will yield a signal less than the decision limit S_D only a small fraction of the time (β).
In practice we do not know the true value of the standard deviation of the errors (σ), so we cannot compute the true decision limit. Also, we do not know the true values of the intercept and slope of the calibration line, so we cannot compute the true detection limit. Instead, we usually set α = β and estimate the decision and detection limits by computing prediction limits for the calibration line and using inverse regression.
The estimated detection limit corresponds to the upper confidence bound on concentration given that the signal is equal to the estimated decision limit. Currie (1997) discusses other ways to define the detection limit, and Glaser et al. (1981) define a quantity called the method detection limit.
A numeric vector of length 2 indicating the signal detection limit and the concentration
detection limit. This vector has two attributes called
simultaneous indicating the values of these arguments that were used in the
Perhaps no other topic in environmental statistics has generated as much confusion or controversy as the topic of detection limits. After decades of disparate terminology, ISO and IUPAC provided harmonized guidance on the topic in 1995 (Currie, 1997). Intuitively, the idea of a detection limit is simple to grasp: the detection limit is “the smallest amount or concentration of a particular substance that can be reliably detected in a given type of sample or medium by a specific measurement process” (Currie, 1997, p. 152). Unfortunately, because of the exceedingly complex nature of measuring chemical concentrations, this simple idea is difficult to apply in practice.
Detection and quantification capabilities are fundamental performance characteristics of the Chemical Measurement Process (CMP) (Currie, 1996, 1997). In this help file we discuss some currently accepted definitions of the terms decision, detection, and quantification limits. For more details, the reader should consult the references listed in this help file.
The quantification limit is defined as the concentration C at which the coefficient of variation (also called relative standard deviation or RSD) for the distribution of the signal S is some small value, usually taken to be 10% (Currie, 1968, 1997). In practice the quantification limit is difficult to estimate because we have to estimate both the mean and the standard deviation of the signal S for any particular concentration, and usually the standard deviation varies with concentration. Variations of the quantification limit include the quantitation limit (Keith, 1991, p. 109), minimum level (USEPA, 1993), and alternative minimum level (Gibbons et al., 1997a).
Steven P. Millard (EnvStats@ProbStatInfo.com)
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Code of Federal Regulations. (1996). Definition and Procedure for the Determination of the Method Detection Limit–Revision 1.11. Title 40, Part 136, Appendix B, 7-1-96 Edition, pp.265–267.
Currie, L.A. (1968). Limits for Qualitative Detection and Quantitative Determination: Application to Radiochemistry. Annals of Chemistry 40, 586–593.
Currie, L.A. (1988). Detection in Analytical Chemistry: Importance, Theory, and Practice. American Chemical Society, Washington, D.C.
Currie, L.A. (1995). Nomenclature in Evaluation of Analytical Methods Including Detection and Quantification Capabilities. Pure & Applied Chemistry 67(10), 1699-1723.
Currie, L.A. (1996). Foundations and Future of Detection and Quantification Limits. Proceedings of the Section on Statistics and the Environment, American Statistical Association, Alexandria, VA.
Currie, L.A. (1997). Detection: International Update, and Some Emerging Di-Lemmas Involving Calibration, the Blank, and Multiple Detection Decisions. Chemometrics and Intelligent Laboratory Systems 37, 151-181.
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Kahn, H.D., W.A. Telliard, and C.E. White. (1998). Comment on “An Alternative Minimum Level Definition for Analytical Quantification” (with Response). Environmental Science & Technology 32(5), 2346–2353.
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# The data frame EPA.97.cadmium.111.df contains calibration # data for cadmium at mass 111 (ng/L) that appeared in # Gibbons et al. (1997b) and were provided to them by the U.S. EPA. # # The Example section in the help file for calibrate shows how to # plot these data along with the fitted calibration line and 99% # non-simultaneous prediction limits. # # For the current example, we will compute the decision limit (7.68) # and detection limit (12.36 ng/L) based on using alpha = beta = 0.01 # and a linear calibration line with constant variance. See # Millard and Neerchal (2001, pp.566-575) for more details on this # example. calibrate.list <- calibrate(Cadmium ~ Spike, data = EPA.97.cadmium.111.df) detectionLimitCalibrate(calibrate.list, simultaneous = FALSE) # Decision Limit (Signal) Detection Limit (Concentration) # 7.677842 12.364670 #attr(,"coverage") # 0.99 #attr(,"simultaneous") # FALSE #---------- # Clean up #--------- rm(calibrate.list)
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