Correction. Errors Caused by Flowrate Variation in High Performance

Correction. Errors Caused by Flowrate Variation in High Performance Size Exclusion Chromatography (GPC). D. D. Bly, H. J. Stoklosa, J. J. KirklandW. W...
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tion with samples stacked over a 10-cm distance within the rabbit and five standards interspaced through the unknowns. The values range from 1 to 12% with an average of about 5%. The variations include all the sources of error that can occur during neutron activation analysis of a sample. We routinely employ this method for the analysis of sea salt aerosols and water samples for major components and biological fluids for both major and minor elements. In the irradiation of sea salt aerosols and water samples, we have had no sample or standards break open during irradiation. This has involved the irradiation of several hundred discs, some for up to 4 hours. The authors have removed filter discs from the sealed plastic for Na, C1, and Br analysis. The blank values for single Whatman 41 filter paper discs are 1.05 f 0.10 pg, 1.29 f 0.01 pg, and 0.005 f 0.002 pg for Na, C1, and Br, respectively. There is a severe deterioration of the filter paper with 50-11 aliquots of any 2N acid solutions, during a 7-hour irradiation, such that removal of the filter disc from the plastic is not possible. The filter paper can still be handled when neutral or basic solutions are used or if the irradiation time is reduced to 4 hours and care is used in handling. Loss of sample to the plastic occurs when aliquots larger than 50 p1 are used and the filters are removed. Loss of halogens (probably as gaseous HCl and HBr) occurs when acid solutions are irradiated for even short periods.

Blood samples have been irradiated for as long as 35 hours and breakage has occurred only when aliquots of between 0.1 to 1.0 ml have been used. In these cases, failures of sealed discs have occurred between 5 to 10% of the time.

ACKNOWLEDGMENT The authors thank A. C. Bachelder and the University of Rhode Island Engineering Instrument Shop for the construction of the apparatus, the staff of the Rhode Island Nuclear Science Center for space and facilities for analysis, and the University of Rhode Island Computer Laboratory for data processing and reduction. RECEIVEDfor review June 23, 1975. Accepted July 25, 1975. This research was supported by the Office for the International Decade of Ocean Exploration, National Science Foundation under NSF-IDOE Grant GX-33777 and by the United States Department of Health, Education, and Welfare, Public Health Service, National Institutes of Health Grant No. 1 R 0 1 HD 06675-02. LITERATURE CITED Jr., Ed., "Guide to Activation Analysis", D. Van Nostrand Co., Inc., N e w York. 1964, pp 14-20. (2) G. H. Friedlander, J. W. Kennedy, and J. M. Miller, "Nuclear and Radio(1) W. S. Lyon,

chemistry", 2nd ed., John Wiley 8 Sons, Inc., New York, 1964, pp 411413.

CORRECTION Errors Caused by Fiowrate Variation In High Performance Size Exclusion Chromatography (GPC)

In this articleby D. D. Bly, H. J. Stoklosa, J. J. Kirkland, and W. W. Yau, Anal. Chem., 47, 1810 (1975), the tabular portions of Figures 1-4 were inadvertently eliminated. These data are essential for following the discussion and

-

% RANDOM VARIATION IN FLOW RATE

Mn MEAN 112,900

0.0

Rw

2aFOR IO RUNS

2uFOR IO RUNS

MEAN

0

278,100

0

0.5

112,900

700

278,100

1,100

I .o

113,000

1,300

278,200

1,900

3.0

I 12,800

4,000

278, I O 0

6,400

5.0

112,600

7,000

277,400

11,200

10.0

I 11,800

Figure 1. Random variation zero to end of GPC curve

12,700

276,500

19,000

in flowrate about a fixed level from time

n

INCREASING FLOW RATE

_..-..

DEVIATION IN

M,

RELATIVE PERCENT ERROR

00

112,900

0.5

113,800

1.0

l14,W

-

INCREASING FLOW RATE dCviiiioN IN FLOW RATE

-

8,

RELATIVE PERCENT ERROR

0.0

112,900

0.0

0.5

114,800

1.7

1.0

123,400

9.3

3.0

146,700

299

RELATIVE PERCENT ERROR

RELATIVE PERCENT ERROR

00

278,100

0.0

112,900

0.8

278,900

0.3

112,100

-0.7

277,300

-0.3

I 5

279,700

06

111.200

-1.5

276,600

-0.5

0.0

278,100

258,400

-71

-23.8

222,600

-20.0 -31.3

-36.8

191,100

43,500

-61.5

128, 7tl)

change in flowrate from time zero to end of

RELATIVE PERCENT ERROR

0.0

PERCENT DEVIATION ,dNRAn

RELATIVE PERCENT ERROR

iin

ii,

-53.7

GPC

DECREASED FLOW RATE RELATIVE PERCENT ERROR

M,

RELATIVE PERCENT ERROR

M,

RELATIVE PERCENT ERROR

0.0

112,900

00

278,100

0.0

112,900

00

278,100

00

0.5

125,030

10.7

305,000

9.1

101,900

-9.7

253,400

-89

1.0

13a.mo

22.4

334,

too

20 J

91,900

-18.6

230, 700

-170

30

2 0 4 , ~

81.0

477.000

715

60,100

-468

157,000

-43 5

672,003

141.6

38,590

-65 9

105, I00

-62 2

II,M)O

-89.7

35,703

-872

107,800

-4.5

273,400

-1.7

104,400

-7.5

270.3W

-2.8

5.0

297,603

1636

-5.7

10.0

716,200

5344

2328

-8.6

86,000 71,300

1.7

262,300

103,203

42.9

2.9

-15 I

-36

100.8

282,900

95,800

0.0

268,100

397,500

286,100

57

278,100

-4.3

558,xx)

7.6

flowrate across the GPC curve

7.6 24.2

0.0

108,000

53.9

4.6

294.W

299,100

345,300

112,900

130.7

118,100

15.2

1.6

#,

173,800

121,500

130, 100

00

RELATIVE PERCENT ERROR

ERROR

260,KK)

3.0

10.0

278,100

282,500

RELATIVE PERCENT

5.0

5.0

Figure 2. Uniform change in

a,,

iNCREASED FLOW RATE

3,

aw

RELATIVE PERCENT ERROR

nw

10.0

DECREASiNG FLOW RATE

Rn

DECREASING FLOW RATE

PFRCFNT

Figure 3. Uniform

PSWFNT ,

FLOW RATE

conclusions on pp 1811-1812. The sketches in the figures illustrate the type of flowrate variation employed while the tabular portion of each curve shows the results obtained. Figures 1-4 are here reproduced in their entirety.

Figure 4. Fixed

ANALYTICAL CHEMISTRY, VOL. 47, NO. 13, NOVEMBER 1975

1,500.xIo 4396

flowrate deviation from specified value