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              50     Modern Analytical Chemistry


                                                  These concerns are illustrated by the Chesapeake Bay monitoring program.
                                              This research program, designed to study nutrients and toxic pollutants in the
                                              Chesapeake Bay, was initiated in 1984 as a cooperative venture between the fed-
                                              eral government, the state governments of Maryland, Virginia, and Pennsylvania,
                                              and the District of Columbia. A 1989 review of some of the problems with this
                                              program highlights the difficulties common to many monitoring programs. 11
                                                  At the beginning of the Chesapeake Bay monitoring program, little attention
                                              was given to the proper choice of analytical methods, in large part because the
                                              intended uses of the monitoring data were not specified. The analytical methods
                                              initially chosen were those standard methods already approved by the EPA. In
                                              many cases these methods proved to be of little value for this monitoring project.
                                              Most of the EPA-approved methods were designed to detect pollutants at their
                                              legally mandated maximum allowed concentrations. The concentrations of these
                                              contaminants in natural waters, however, are often well below the detection limit
                                              of the EPA methods. For example, the EPA-approved standard method for phos-
                                              phate had a detection limit of 7.5 ppb. Since actual phosphate concentrations in
                                              Chesapeake Bay usually were below the EPA detection limit, the EPA method
                                              provided no useful information. On the other hand, a nonapproved variant of
                                              the EPA method commonly used in chemical oceanography had a detection limit
                                              of 0.06 ppb. In other cases, such as the elemental analysis for particulate forms of
                                              carbon, nitrogen, and phosphorus, EPA-approved procedures provided poorer
                                              reproducibility than nonapproved methods.




                  3 H KEY TERMS


              accuracy  (p. 38)                 measurement  (p. 36)              rugged  (p. 42)
              analysis  (p. 36)                 method  (p. 36)                   selectivity  (p. 40)
              analytes  (p. 36)                 method blank  (p. 45)             selectivity coefficient  (p. 40)
              calibration  (p. 47)              precision  (p. 39)                sensitivity  (p. 39)
              calibration curve  (p. 47)        procedure  (p. 36)                signal  (p. 37)
              concentration techniques  (p. 38)  protocol  (p. 37)                standardization  (p. 47)
              detection limit  (p. 39)          quality assurance and quality     technique  (p. 36)
              determination  (p. 36)             control  (p. 48)                 total analysis techniques  (p. 38)
              matrix  (p. 36)                   robust  (p. 42)                   validation  (p. 47)



                  3 I SUMMARY


              Every discipline has its own terminology. Your success in studying  ple, time, cost, and the availability of equipment. These criteria are
              analytical chemistry will improve if you master the language used  not mutually independent, and it often is necessary to find an ac-
              by analytical chemists. Be sure that you understand the difference  ceptable balance among them.
              between an analyte and its matrix, a technique and a method, a  In developing a procedure or protocol, consideration is given
              procedure and a protocol, and a total analysis technique and a  to compensating for interferences, calibrating equipment and
              concentration technique.                           standardizing the method, obtaining an appropriate sample, and
                An analytical method is selected on the basis of criteria such as  validating the analysis. Poorly designed procedures and protocols
              accuracy, precision, sensitivity, selectivity, robustness, ruggedness,  produce results that are insufficient to meet the needs of the
              the amount of available sample, the amount of analyte in the sam-  analysis.
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