1070-4272/05/7809-1408C2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 9, 2005, pp. 1408!1410. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 9,
2005, pp. 1433!1435.
Original Russian Text Copyright + 2005 by M. Gavrilenko, N. Gavrilenko, Mokrousov.
OF SYSTEMS AND PROCESSES
Solid-Phase Extraction of Aliphatic Amines
from the Aqueous Phase with a Methacrylate Polymer
M. A. Gavrilenko, N. A. Gavrilenko, and M. G. Mokrousov
Tomsk State University, Tomsk, Russia
Received December 30, 2004; in final form, April 2005
Abstract-Solid-phase extraction of aliphatic amines from aqueous solutions with a methacrylate polymer
was studied. The possibility of simultaneous sorption of amines considerably differing in the boiling point
Aliphatic amines widely occur in the nature. They
act as secondary pollutants forming by biodegradation
of nitrogen-containing compounds, including proteins
and amino acids . The necessity of monitoring
amines is caused not only by an unpleasant odor of
some of them, but also by the possibility of their
transformation under certain conditions into consider-
ably more hazardous nitrosamines .
Toxic amines are particularly hazardous in aquatic
objects . Owing to high polarity, amines are readily
soluble in water, and their recovery is difficult.
Amines are usually determined by capillary gas and
liquid chromatography [4, 5]. Despite high sensitivity
of these methods, determination of amines requires
preconcentration. This is usually done by liquid [6, 7]
and solid-phase [8, 9] extraction. A relatively new
approach is solid-phase preconcentration of amines on
the microlevel  involving the use of a detector
highly selective to nitrogen. Also, Baltussen et al.
[11, 12] suggested a combined approach involving
solid-phase extraction with polydimethylsiloxane or
poly(butyl acrylate) followed by thermal desorption
into the chromatograph injector. However, nonpolar
sorbents poorly extract polar amines, and polar poly-
(butyl acrylate) in the step of thermal desorption gives
noise and false peaks in the chromatograms.
The use of styrene3divinylbenzene polymers, XAD,
and cyclodextrins for solid-phase extraction of amines
was described in numerous papers , but no ac-
ceptable procedure has been developed. Thus, studies
in the field of sorption of polar substances from aque-
ous media remain very urgent.
In this study we examined solid-phase extraction of
dimethylamine (DMA), ethylamine (EA), diethylam-
ine (DEA), triethylamine (TEA), propylamine (PA),
dipropylamine (DPA), and tripropylamine (TPA) from
aqueous solutions with a polar hydrophobic methacry-
late polymer (PM), followed by determination of the
amines by capillary gas chromatography.
The study was performed with a Shimadzu GC-9A
gas chromatograph (Japan); a 25000 0 0.25-mm capil-
lary column was coated with SE-30 (30 mm). The
temperature of the detector and injector was 200oC.
The column temperature program was as follows:
70oC, 1 min; heating to 200oC, 5 deg min
3 min. The sample was pumped through the sorbent
with a Gilson Minipuls-2 micropump (the United
Stock solutions of amines (1 g l
) were prepared
in MILLI-Q water (Millipore, the United States) and
were stored at 6oC. Working solutions (20350 mgl
were prepared just before the experiments in double-
distilled water. Acidic solutions (pH < 4) were pre-
pared with hydrochloric acid. The buffer solution with
pH 9 was prepared by mixing 0.1 M solutions of po-
tassium dihydrogen phosphate and sodium hydroxide.
The polymethacrylate sorbent was prepared by
radical block copolymerization of methacrylate mono-
mers, with benzoyl peroxide as initiator . A 10 0
5-mm steel precolumn was packed with the sorbent
of particle size 0.130.15 mm. Aqueous solutions of
DMA, EA, DEA, TEA, PA, DPA, and TPA (50 mgl
each) were passed through the PM sorbent at pH 9.
To evaluate the extractive power, we took 10 ml of
the solution that passed through the sorbent and the
same aliquot of the initial solution. Both samples were
extracted with 1 ml of diethyl ether. The extracts were
dried over anhydrous sodium sulfate and evaporated
to 100 ml prior to the analysis. Before extraction of