8O
6O
o
40
.ID
20
o
G
~ 3
C
-- 2
1
0
0
(b)
o
o
o
o
o
o
o
0
0
0
0
0
0
(a)
S
S
R
3
o
o o o o
A
10 30 50 70 90
Temperature/°C
FIG. 4. Temperature dependencies of the integrated band intensities
of the second (a) and first (b) overtones of the OH stretching mode
for the monomeric form of Z-9-octadecen-l-ol. (~) Data from the raw
spectra (after density correction); (A) data from the difference spectra.
Fig. 4b. The intensities in both Fig. 4a and 4b increase
with increasing temperature in the same way.
In the present study results based on both the second
and first overtone seem to be reliable. Both the second
and first overtones of the OH stretching mode of the
monomeric form can probably be used to monitor the
spectral changes. However, the use of the second over-
tone might be more convenient because one can deter-
mine accurate integrated intensity in an easier way.
CONCLUSION
The present paper demonstrates that the second over-
tone of the OH stretching mode of the monomeric form
of Z-9-0ctadecen-l-ol in pure liquid is very useful for
probing the temperature-dependent change in the in-
tegrated intensities, which is related to the dissociation
of hydrogen-bonded alcohols. More thorough NIR stud-
ies of the structure and thermodynamic properties of
alcohols are now in progress in our group and will be
reported soon.
1. M. Iwahashi, N. Hachiya, Y. Hayashi, H. Matsuzawa, M. Suzuki,
Y. Fujimoto, and Y. Ozaki, J. Phys. Chem. 97, 3129 (1993).
2. M. Iwahashi, Y. Hayashi, N. Hachiya, H. Matsuzawa, and H. Ko-
bayashi, J. Chem. Soc. Faraday Trans. 89, 707 (1993).
3. M. A. Czarnecki, Y. Liu, Y. Ozaki, M. Suzuki, and M. Iwahashi,
Appl. Spectrosc. 47, 2162 (1993).
4. B. G. Osborne and T. Fearn, in Near In[rared Spectroscopy in Food
Analysis (John Wiley & Sons, New York, 1986), p. 21.
5. Near-Infrared Technology in the Agricultural and Food Industries,
P. Williams and K. Norris, Eds. (American Association of Cereal
Chemists, St. Paul, Minnesota, 1990), p. 17.
6. A. S. Banana, and P. R. Griffiths, J. Near Infrared Spectrosc. l, 13
(1993).
7. V. Zanker, Z. Phys. Chem. 200, 250 (1952).
Comment on a "Simple and Efficient
Method to Eliminate Spike Noise
from Spectra Recorded on
Charge-Coupled Device Detectors"
WIELAND HILL
Institut fEr Spektrochemie und angewandte Spek-
troskopie (ISAS), P.O. Box 101352, 44013 Dortmund,
Germany
Index Headings: Computer applications; Raman spectroscopy.
INTRODUCTION
Recently, Takeuchi et al. proposed a simple, so-called
"robust summation" method for the efficient elimination
of spike noise from charge-coupled device (CCD) data. 1
In their paper, robust summation was shown to be ad-
vantageous in comparison to median filters, which had
been occasionally employed to remove spikes from data
recorded with CCD detectors. 2
In our opinion, missing-point fitting is the most ad-
vanced method for spike removal. 3-5 Even the algorithm
by Phillips and Harris 3 is superior to the use of median
filters and robust summation with regard to several fea-
tures.
DISCUSSION
Missing-point correction of spikes is based on a com-
parison of measured values with estimates calculated
from a number of neighboring data points within the
same spectrum or within successively recorded spectra.
The point in question, as well as identified neighboring
spikes, is deleted for the calculation of these estimates.
By this algorithm, accurate estimates are obtained and
can be used for efficient spike correction.
Robust summation is based on a comparison with a
single neighboring value measured on the time axis. In
comparison to missing-point fitting, this principle has
the disadvantages described below.
The standard deviation of the measured neighboring
values is generally larger than that of missing-point es-
timates. This factor leads to less reliable spike identifi-
cation. Consequently, a higher proportion of unspiked
data points need to be "corrected."
Generally, it is unknown whether the consecutively
recorded spectra contain exactly the same spectral in-
formation. The proposed scaling, using the total intensity
of each spectrum, 1 compensates for intensity fluctuations
due to laser instabilities or changing adjustments. Other
disturbances, such as changing stray room light, changing
fluorescence background due to a degradation of fluo-
rescent impurities, or imperfect beam pointing onto an
inhomogeneous sample, may further seriously influence
the results of the spike correction by this method. Fur-
Received 19 March 1993; revision received 18 June 1993.
Volume 47, Number 12, 1993 0~3-7028/93/4712-217152.00/0 APPLIED SPECTROSCOPY 2171
© 1993 Society for Applied Spectroscopy