Journal of the Arkansas Academy of Science

Volume 47 Article 19

1993

Ultraviolet Spectra of Acetic Acid, Glycine, and

Glyphosate
J. Scott McConnell
University of Arkansas at Monticello

Rose M. McConnell
University of Arkansas at Monticello

Lloyd R. Hossner
Texas A&M University

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Recommended Citation
McConnell, J. Scott; McConnell, Rose M.; and Hossner, Lloyd R. (1993) "Ultraviolet Spectra of Acetic Acid, Glycine, and
Glyphosate," Journal of the Arkansas Academy of Science: Vol. 47 , Article 19.
Available at: http://scholarworks.uark.edu/jaas/vol47/iss1/19

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 Journal of the Arkansas Academy of Science, Vol. 47 [1993], Art. 19

J. Scott McConnell Rose M.McConnell

Southeast Research 8c Extension Center Division ofMath 8c Science
University of Arkansas University of Arkansas-Monticello
Monticello, AR 71656 Monticello, AR 71656
LloydR. Hossner
Department of Soil & Crop Science
Texas A&MUniversity
College Station, TX 77843
Abstract

The influence of pH on the ultraviolet spectra of 0.001, 0.005, and 0.010 Mglyphosate, glycine, and acetic acid was
investigated. Each dilution of each acid was adjusted to acidic, neutral, and basic pH values. Ultraviolet spectra were
recorded from 300 to 200 nm for each acid-dilution-pH combination. The wavelength of maximum absorption (A^.^) of
glyphosate and glycine was slightly higher in the high pH solutions than in the neutral and low pH solutions. The A^^ of
acetic acid was apparently unaffected by changes inpH. Molar extinction coefficients (e) at Xmax increased with pH for all
three acids. Regression analysis of the absorbance versus concentration for each acid-pH combination indicated linear
relationships. Coefficients of determination (r*) were greater than 0.88 at both 210 and 215 nm for all acids and pH val-
ues.

Introduction the analytical determination of glyphosate thereby

demonstrating its importance (Burns, 1983; McConnell
(UV) spectroscopy of organic compounds and Hossner, 1985; Errata, 1991).

IJltraviolet
tally indicates little about structural characteristics,
ganic compounds that contain certain functional
>ups such as carboxyls, carboxylates, aldehydes, o OH
ones, and esters have UV absorption maxima in the
ge of 190 to 210 nm. UV spectra of these moieties are HO-C-CH 2 -NH-CH2 -P-OH
; as diagnostic as infrared spectra, but may be used in
intifying the chromophore bearing species (Willard, et
1974). The mechanism of UV radiation absorption of
O
se single chromophores is the excitation of p-orbital Fig. 1. Glyphosate
vbonding electrons to antibonding a-orbitals as well as
? 71* of the carboxylate carbon. The transitions are n -> The objective of this research was to examine the UV
and 7C -> 71*, and occur on the carbon-oxygen unsatu- spectra of glyphosate and two other carboxylic acids, and
:d bonds (Parikh, 1974; Scott, 1964). determine the wavelength of maximum absorbance (X^^)
Glyphosate, or N-phosphonomethyl glycine, (Fig. 1), is and the molar extinction coefficients (e) at Xn,^ 215 nm,
an organic acid and the active ingredient inthe herbicide and 210 nm as influenced by pH. Further, regression
R marketed by the Monsanto Chemical analysis was used to determine the linearity of graphs of

Iundup
rporation. The rapid adsorption of glyphosate by soils UV absorbance at 210 and 215 nm versus acid concentra-
Isoil compounds has made the compound the focus tion.
many studies (Hance, 1976; Sprankel et al., 1975;
rstensson and Amisep, 1977). Generally, these studies
re shown glyphosate to be strongly adsorbed by soils Materials and Methods
isoil constituents under a variety of conditions,
rtain studies have been conducted to examine the UV
—
Organic Acids. Glyphosate (99%) was obtained from
:ctra of solution-phase, glyphosate-metal complexes the Monsanto Chemical Corporation and used without
1 have failed to show the contribution of the uncom- further purification. Reagent grade glycine and acetic
xed carboxyl and carboxylate groups of glyphosate acid where purchased from Fischer Scientific Supply of
ass, 1984; Glass, 1987; McBride and Rung, 1989). The Piano, Texas and also used without further purification.
absorption of the acid functionality has been used in Dilutions of acetic acid were quantified with titrametric

Proceedings Arkansas Academy of Science, Vol. 47, 1993

73

Published by Arkansas Academy of Science, 1993 73

 Journal of the Arkansas Academy of Science, Vol. 47 [1993], Art. 19
P acih, v^iycine, ana oiypnosaie

techniques with standard base. Samples of the acids were

then diluted to 0.010, 0.005, and 0.001 M. Each sample
was adjusted to pH values near 3, 7, and 10 with NaOH.
—
Instrumentation. The ultraviolet spectra of the proto-
nated and deprotonated acids at the three concentrations
were recorded from 300 to 200 nm on a Perkin-Elmer
Model 25 UV-visible spectrophotometer. Matched silica-
quartz cuvettes with a 1.0 cm path length from Perkin-
Elmer (Lot Number 14993) were used to contain the
diluted acids. Scan speed was set at 20 nm/min. and 1.0
-
nm/in. The spectra of the 0.010 Msolutions were used to
determine the A.max the absorbance maxima, and the £ at
A-max*
The absorbances and e of the samples were also
recorded at 210 and 215 nm, and analyzed using linear
regression. Regression analysis gave estimates of slopes
and intercepts, and the linearity of the relationship
between absorbance and concentration for each acid and
pH.

Results and Discussion

Spectra of all three compounds at the three concentra-

tions and pH values indicate UV absorbance from
approximately 220 to below 200 nm. This is the approxi-
mate wavelength range organic acids are expected to Fig. 2. Absorbance spectra of 0.010 M glyphosate solu-
tions adjusted to pH 2.83, 7.01, and 10.01.
absorb UV radiation (Willard et al., 1974). The total
absorbance spectra of 0.010 M solutions of glyphosate
increased with pH and exhibited a shift in absorption
Table 1. Wavelength of maximum absorption (X^^), max-
maxima from <200 nm (pH 2.83 and 7.01) to 214 nm
pH 10.01) (Fig. 2). These results disagree with reports
imum absorbance (Amax), and molar extinction coeffi-
that state glyphosate is UV transparent (Glass, 1984; cient (£max ) of ultraviolet spectra of 0.010 M solutions of
Glass, 1987).
glyphosate, glycine, and acetic acid at low, neutral, and
high pH values.
The Xroax for the low and neutral pH solutions of 0.010
4 glyphosate and glycine was found to be near or below
200 nm. As the pH was increased, the X,max of glyphosate
Glyphosate Glycine Acetic Acid
and glycine increased to 214 and 210 nm, respectively.
pH
The acetic acid solutions exhibited X^^ at 204, 200 and
204 nm for the low, neutral and high pH solutions,
respectively (Table 1). The trend of increasing pH and 2M 1Q1 10.01 3.03 6.99 9.97 3.49 6.94 10.13

ncreasing Xmax that was evident in the spectra of Jlmax <200 <200 214 <200 201 210 204 200 204

jlyphosate and glycine was not observed with acetic acid °-430 °-615 °-510 °-650 °-325 °-670 °-885
Amax L37 116
>ecause of its monoprotic structure. Amino acids and
diacids differ from monoprotic acids in that they general- 62 137 65 116 33 89
emax 43 51 67
y show an increase in absorbance and a shift to longer
wavelengths (bathochromic shift) with increasing pH
Greenstein and Winitz, 1961; Parikh, 1974). The The £ at the A,max (£max) for all three acids was found to
ncrease in absorbance and the bathochromic shift are range between 33 and 137, and increase with increasing
attributed to the auxochrome created by dianionic struc- pH (Table 1). Three groups of similar 6^,^ are apparent,
ures. The X,max of monoprotic acetic acid remained rela-
and related to the solution pH. The low pH solutions of
ively constant with increasing pH due to absence of any glyphosate, glycine and acetic acid had similar £max that
auxochromes.

Proceedings Arkansas Academy of Science, Vol. 47, 1993

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 Journal of the Arkansas Academy of Science, Vol. 47 [1993], Art. 19

ranged from 33 to 51. All three emax were found to The mean of the slopes of the regression lines (215
increase slightly, ranging from 62 to 67, as the pH was nm) for low and neutral pH solutions of glyphosate and
raised from acid to neutral. Increasing the pH of the solu- glycine, and all three acetic acid solutions was 18.20 with
tions to near 10 resulted in large increases in emax with a standard deviation of ± 3.07. The range of the slopes
increasing pH, up to 89, was found with the acetic acid for these solutions was from 13.59 to 23.39, thereby indi-
solutions. The large increases in the emax values of the cating little difference in the slopes of these regression
glyphosate and glycine solutions indicate that the addi- lines. Solutions of high pH glycine and glyphosate had
tional lone pairs of electrons present in the phospho- much higher slopes than their lower pH analogs or the
amide of glyphosate and the amino group of glycine act acetic acid solutions. This corresponds with the increases
as an auxochrome causing both a bathochromic shift and in e max and changes in Xmax observed in the UV spectra of
an increase in absorbance. The degree of protonation of the high pH glyphosate and glycine solutions. The
these auxochrome groups generally affects the availability increased absorbance of the high pH glycine and
of the lone pairs of electrons for n -» n* transitions glyphosate solutions increased the slope of the regression
(Parikuh, 1974). These experimental results demonstrate line.
that the degree of protonation is a major determinant of
the UV absorption characteristics of glyphosate, glycine
and acetic acid. Conclusions
Regression analysis of the concentrations of the indi-
vidual acids and their UV absorptions indicated a high Solutions of glyphosate, glycine, and acetic acid were
degree of linearity at 210 and 215 nm for the three pH shown to absorb ultrviolet radiation from 220 to 200 nm.
values tested (Fig. 3). The r2 exceeded 0.9 in all regres- Wavelength of maximum absorption and e max for
sion lines at 215 nm, and in all but one at 210 nm. The glyphosate and glycine were similar at low and neutral
high degree of linearity indicates that these wavelengths pH. Increased pH resulted in increased Xmax and £max .
may be used for analytical determinations of glyphosate, The Xmax of the acetic acid solutions was seemingly unaf-
glycine, or acetic acid in aqueous solutions. The presence fected by pH, while the emax was less affected by pH than
ofother carboxylic acids or mixtures of these three would the other acids.
probably interfere in this type analysis unless a suitable Regression analysis of the concentrations of the acids
separations technique were employed. and their UV absorbances indicates a linear relationship

Fig. 3. Slope, intercept, and coefficient of determination (r2) of absorbance versus concentration of glyphosate, glycine,
and acetic acid at high pH (AH), moderate pH (AM), and low pH (AL) values.

Proceedings Arkansas Academy of Science, Vol.47, 1993

Published by Arkansas Academy of Science, 1993 75

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 Journal of the Arkansas Academy of Science, Vol. 47 [1993], Art. 19

at 210 and 215 nm. The slopes of the regression lines

were found to be similar for low and neutral pH solu-
tions of glyphosate and glycine, and for all acetic acid
solutions. Much higher slopes were found for high pH
solutions of glyphosate and glycine. The linear relation-
ship between concentration and UV absorbance of
glyphosate provides a useful analytical method for the
determination of glyphosate, and similar acids, in aque-
ous solutions.

Literature Cited

Burns, A.J. 1983. Liquid Chromatographic

Determination of glyphosate Technical and Its
Formulation: Collaborative Study. J. Assoc. Off. Anal
Chem. 66:1214-1219.
Errata. 1991. J. Agric. Food Chem. 39: 824.
Glass, R.L. 1984. Metal Complex Formation by
Glyphosate. J. Agric. Food Chem. 32:1249-1253.
Glass, R.L. 1987. Adsorption of Glyphosate by Soils and
Clay Minerals. J. Agric. Food Chem. 35: 497-500.
Greenstein, J.P. and M. Winitz. 1961. Chemistry of the
Amino Acids, Volume 2. p. 1689. Robert E. Krieger
Publishing Co.: Malabar, FL.
Hance, R.J. 1976. Adsorption of Glyphosate by Soils.
Pesticide Sci. 7: 363-366.
McBride, M. and K.H. Kung. 1989. Complexation of
r glyphosate and related ligands with iron (III).Soil Sci.
Soc. Am.J. 53: 1668-1673.
McConnell, J.S. and L.R. Hossner. 1985. pH
Dependent Adsorption Isotherms of Glyphosate. J.
Agric. Food Chem. 33: 1075-1078.
Parikh, V.M.1974. "Ultraviolet Spectroscopy. In
Absorption Spectroscopy of Organic Molecules.
Addison- Wesley Publishing Co.: Reading, MA.
Scott, A.I.1964. Single Chromophores. In
Interpretation of the Ultraviolet Spectra of Natural
Products. Pergamon Press, New York, NY.
Sprankel, P., W.F. Meggitt and D. Penner. 1975.
Adsorption, Mobility, and Microbial Degradation of
Glyphosate by Soils. Weed Sci. 23: 229-234.
Torstensson, N.T.L. and A.A. Amisep. 1977.
Detoxification of Glyphosate inSoils. Weed Res. 17
209-212.
Willard,H.H., L.L.Merritt,Jr. andJ.A. Dean. 1974.
Ultraviolet and Visible Absorption Methods. In
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