the concentration reported by NET Pacific, Inc.

that both QC and QA laboratories follow the same

(Fig. 12), the correlation was significant at the

extraction and analysis procedures. Finally, we rec-

ommend stopping the dual use of laboratories

indicates no bias (log ratio = 0.0) at a TPH con-

for QA and QC functions.

centration of 5600 ppm. At lower TPH concentra-

tions, CAS, Inc. reports concentrations on sample

splits that exceed those reported by NET Pacific,

The 71 data reports for explosives in soils sub-

Inc., and the difference increases as concentration

mitted by the MRD contained a total of 65 pairs

decreases. For example, when NET Pacific, Inc.

with both QC and QA as real numbers. The dis-

reports a TPH concentration of 100 ppm, CAS,

tribution of these pairs among several analytes is

Inc. reports, on average, a concentration of 200

shown in Table B6. The MRD, Omaha, Nebraska,

ppm. Bias of this magnitude is unacceptable. Be-

laboratory served the QA function in all of these

cause of the numerous laboratories used to ana-

results. Seven of the 65 pairs (10.8%) yielded QC/

lyze samples, this problem is magnified several

QA ratios outside 0.254.00. However, clustering

times. In the case of the NPD results, the 43 ratios

around the ideal ratio of 1.00 was much better

not shown in Figure 12 contained results from

than for VOCs or TPH; 72% were between 0.50

five other laboratories.

2.00. Bias was suggested because 41 of the 65 ra-

One possible way to identify the source of bias

tios were less than 1.00. Since there was no ap-

and, hopefully, to eliminate it, is to prepare sev-

parent distinction in the distributions or geometric

eral typical soils fortified with known concentra-

means of the ratios for individual analytes, they

tions of TPH. To minimize potential error sources

were treated as a single group. Figures 13 and 14

such as volatilization and biodegradation, we sug-

show a histogram and a probability plot, respec-

gest weighing portions of homogenized dry soils

tively, for the logs of the 58 ratios between 0.25

into ampoules. Each ampoule would be spiked

4.00. The lognormal model once again provides a

with a known amount of TPH and sealed as de-

reasonable fit.

scribed by Hewitt (1994). Perhaps three soils with

different clay and organic matter content could

20

be used. After participating laboratories analyzed

these secondary standards and submitted the re-

sults for statistical analysis, a general meeting

could be held to resolve causes of large differ-

Boundaries Corresponding to

Ratios of 0.25 to 4.00

ences. Ideally the number of participating labo-

15

ratories would be minimized. Unfortunately,

there is no obvious way to compensate for the

effects of variable degrees of weathering, and

that may prove to be one of the largest sources

10

of error.

In summary, we think it is inappropriate to

suggest acceptability limits until the method as

currently practiced is brought under better con-

trol. If temporary limits are desired for the in-

5

terim, we feel they should be no wider than 0.25

4.00. When these limits were used for the most

recent results for 87 samples from 15 project lo-

cations, 5.5% of the QC1/QC2 ratios and 16% of

0

the QC/QA ratios were outside of these limits.

These results agree well with the 6.0% and 14%

estimates obtained for archived NPD data.

As soon as possible, secondary TPH standards

should be prepared for use in a study to define

and minimize bias. Such standards could also

QC

Logs of

Concentration Ratios

QA

become part of the routine QC program. A study

of sampling, sample splitting, and storage should

also be conducted. It is also important to ensure

15