7.

3
II.7.3 Glufosinate and
glyphosate
by Yasushi Hori and Manami Fujisawa

Introduction

Non-selective phosphorus-containing amino acid-type herbicides (PAAHs) to be used for foli-

age exhibit lower toxicities than paraquat and are easily obtainable; they, thus, have come into
wide use since 1980. The PAAHs include glufosinate (GLUF), glyphosate (GLYP) and biala-
phos (BIAL). In Japan, there are many kinds of products containing GLUF and GLYP com-
mercially available, and the number of suicidal cases using them is increasing [1].
In acute poisoning by GLUF, there is a latent period for 4–60 h before appearance of poi-
soning symptoms, such as lowered consciousness levels, respiratory arrest and generalized
convulsion; when more than 100 mL of BASTA Fluid® (GLUF, 18.5 %; anion surfactant; blue-
green in color) is ingested, the physical conditions of the victim are seriously aggravated with
high incidence [2]. Respiratory controls, such as securance of the respiratory tract and artificial
respiration, are very important for rescuing such victims. Since it is possible to predict the
aggravation of the GLUF poisoning for a victim from the time after its ingestion and from a
blood GLUF concentration [3], the rapid analysis of blood GLUF becomes very meaningful
not to miss the timing for starting the respiratory control; it is critical to prevent a victim from
falling into the unfortunate turning point.
For analysis of GLUF and GLYP in biomedical specimens, various methods by a modified
technique of the standard GC-NPD with N-acetyl and O-methyl derivatizations [4], GC/MS
using tert-butyldimethylsilyl (t-BDMS) derivatization [5–7], TLC [8], HPLC with fluorescence
detection after post-column derivatization using o-phthalaldehyde [9], HPLC with fluores-
cence detection after pre-column derivatization using 9-fluorenylmethyl chloroformate
(FMOC-Cl) [10], HPLC with UV detection after pre-column derivatization using phenyl iso-
thiocyanate [11], ion chromatography with electrochemical detection without any derivatiza-
tion [12], LC/MS with N-acetyl and O-methyl derivatizations [13] and HPLC with UV detec-
tion after pre-column derivatization using p-nitrobenzoyl chloride [14] were reported.
In this chapter, some details on GC/MS [7], HPLC with fluorescence detection [10] and
HPLC-UV [14], after each derivatization for analysis of PAAHs, are described.

GC/MS analysis [7]

Reagents and their preparation

• GLUF (DL-homoalanin-4-yl(methyl)phosphinate monoammonium salt) and its metaboli-

te 3-methylphosphinicopropionic acid (MPPA) can be purchased from Wako Pure Chemi-
cal Industries, Ltd., Osaka, Japan; GLYP (N-(phosphonomethyl)glycine) and its metabolite

© Springer-Verlag Berlin Heidelberg 2005