Empirical techniques using laboratory-based Near Infrared Spectroscopy (NIRS) have been developed to determine protein, carbohydrate, and other biochemical contents from dried plant materials (Marten et al., 1989; Barton et al., 1992). However, because the spectrum of water dominates fresh leaf reflectance (Elvidge, 1990), it remains to be determined whether these biochemicals can be detected in living plant material at the leaf level and at the canopy level.
This study investigates whether the carbon, cellulose, nitrogen, lignin,
water, and dry weight composition of fresh leaves can be detected using
the infrared reflectance at the leaf level.
Immediately after sampling, reflectance measurements were made with an NIRS spectrometer. Measurements were made between 400-2498 nm at 2 nm intervals with a full width-half maximum slit width of 10 nm, although this study only reports the results from the infrared portion of the spectrum. One standard sized leaf disk was punched from each leaf, weighed, and backed with a black background for reflectance measurements. Following reflectance measurements, leaf disks were weighed, wrapped in aluminum foil, frozen in liquid nitrogen, lyophilized, weighed and electronically scanned for area measurement. The difference in weight between fresh and dried sample was attributed to water content.
An additional 15-20 leaves (bulk samples) of each plant species were wrapped in aluminum foil and frozen in liquid nitrogen for later biochemical analysis. The samples were stored on dry ice during transport, lyophilized, and ground through a 1 µm screen using a ball mill grinder. Leaf powders were stored at -70oC, desiccated.
A subset of the lyophilized bulk samples were sent to the laboratory
of Dr. John Aber, University of New Hampshire for biochemical analysis.
Total carbon and nitrogen were determined with a Perkin-Elmer 2400 CHN
Elemental Analyzer. Cellulose and lignin were determined by proximate analysis,
a technique of sequential extractions in dichloromethane, water and sulfuric
acid. The sulfuric acid fraction represents cellulose and the residue represents
lignin (Effland, 1977).
In all cases, more of the variance was explained when the chemistry data were expressed on a content (g/unit area) basis than when they were expressed on a concentration (g/g) basis. This probably resulted from the fact that the spectrometer beam probes the leaf on an area basis.
The bands selected by the regressions differed depending upon whether log(1/R), first derivative or second derivative were used. Similar to the findings of Curran et al. (1992), the selected bands rarely corresponded to known features for the chemical being examined. In addition, band selection was heavily dependent upon the basis on which the chemistry was expressed. The bands selected for regressions of each chemical on dry weight and area bases coincided less than 10% of the time.
Wessman et al. (1988) found that the nitrogen concentration of dry leaves was best predicted using the first derivative of log(1/R) and that lignin concentration was best predicted using the second derivative of log(1/R). Using their coefficients on our dataset explained 64% of the variance in nitrogen concentration but none of the variance in lignin concentration. Thus, at least for lignin, the coefficients selected in that study were not useful with the present dataset.
Several lines of evidence suggest that correlations obtained from multiple linear regressions lack robustness for estimates of the biochemical contents or concentrations of fresh leaves. These are the lack of relationship between the bands selected and known absorption features, the inconsistency with which bands are selected, and the lack of a significant regression using lignin coefficients from another study. In addition, the majority of the spectral information is lost when using multiple linear regression with a small number of regressors.
Principal components analysis reduces the dimensionality of the reflectance data while preserving the information represented by reflectance in each of the 850 spectral bands between 800 and 2498 nm. Stepwise multiple linear regression using the first five principal component scores for each reflectance spectrum and the biochemistry dataset explained 49-91% of the variance in the chemistry content (area basis) and 23-69% of the variance in the chemistry concentration (dry weight basis), except that no significant regression was found for cellulose concentration. For all chemicals, more of the variance was explained by regressions using principal component scores for content rather than concentration (Table 4).
Principal components analysis was also used to remove the effects of
water spectrum by summing the product of the water content (g/m2)
of each sample and log(1/T) (Norris and Williams, 1987) for water for each
band and partialling this sum out of the analysis. The first five principal
components explained 99.8% of the variance in the spectral dataset. Stepwise
multiple linear regression using the first five principal component scores
explained 40-82% of the variance in the chemistry content and 40-62% of
the variance in the chemistry concentration, except that no significant
regression was found for cellulose concentration. Removing the water spectrum
improved the fits for carbon, nitrogen, and lignin concentration by 24,
15 and 5% respectively, and improved the fit for nitrogen content by 12%.
Removing the water spectrum degraded the fits for carbon, cellulose, lignin,
and leaf content by 2, 9, 3 and 4% respectively.
Acknowledgments
This research was performed under NASA NAS5-31359 and NAS5-31714. The
computer analyses were performed on Digital Equipment Corporation DEC 5000
and DEC Alpha computers provided under the Sequoia 2000 research program.
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