Fresenius J Anal Chem (1997) 359 : 285–287
O R I G I N A L PA P E R
H.-J. Neu · R. Sprenger
Trace analysis of epichlorohydrin in water samples
Received: 20 February 1997 / Revised: 11 April 1997 / Accepted: 15 April 1997
Abstract According to a recent proposal of a new coun-
cil directive of the Commission of the European Commu-
nity concerning the quality of water intended for human
consumption, the maximum concentration of epichlorohy-
drin allowed in potable water is intended to be limited to
0.5 µg/L. To our knowledge no practical analytical tech-
nique for routine analysis purposes of aqueous samples is
available at present. In this paper an analytical method is
described using solid phase extraction (SPE) for the en-
richment of epichlorohydrin from water samples with
subsequent determination by gas-liquid chromatography
with electron capture detection. Quantitative recovery was
achieved. Using a sample volume of 100 mL a detection
limit of 0.1 µg/L can be reached. The method has suc-
cessfully been applied to the analysis of epichlorohydrin
in tap water, surface water and waste water.
1 Introduction
Due to its toxicity epichlorohydrin has been listed for
many years by the Commission of the European Commu-
nity among compounds dangerous for the water environ-
ment. In a new proposal for a council directive concerning
the quality of water intended for human consumption,
epichlorohydrin is listed with a limiting value of 0.5 µg/L
in potable water. At present no practical routine analytical
technique is available for the determination of epichloro-
hydrin in water samples at such low concentrations. The
problem with the analysis of epichlorohydrin in water
samples mainly arises from its high solubility in water (66
g/L) [1], preventing an effective enrichment by the usu-
ally applied techniques using extraction with lipophilic
media or by vapour phase techniques. Furthermore, the
hydrolytic behaviour of the substance has to be taken into
Dedicated to Professor Dr. Karlheinz Ballschmiter
on the occasion of his 60th birthday
H.-J. Neu · R. Sprenger (Y)
BASF Aktiengesellschaft, Umweltanalytik,
D-67056 Ludwigshafen, Germany
© Springer-Verlag 1997
account. According to data published in the literature the
half-life of epichlorohydrin in water at a pH of 7 and
20° C is only 6.2 days [2]. At higher or lower pH the sta-
bility is much lower.
Methods for the analysis of epichlorohydrin in water
described in the literature are based on sample pretreat-
ment by static or dynamic headspace techniques [2, 3] or
liquid-liquid extraction using hexane [4] or diethylether
[5], followed by gas-liquid chromatography with ECD or
MS-detection. As far as detection limits are cited in the
literature they range from 1 to 50 µg/L. The most sensi-
tive technique seems to be given by a purge and trap pro-
cedure using a water volume of 200 ml to which 60 g of
Na2SO4 is added followed by a stripping with a helium
flow of 25 mL/min over 20 min [3]. The purged analyte is
trapped by a Tenax® column from which it is thermally
desorbed by heating the trap to 200°C for 8 min. During
this time the analytes are transferred to the inlet of a GC-
column where cryofocussing of the organic vapour takes
place. Chromatographic separation is started by applying
a temperature program to the GC-column. The yield of
this complicated gas extraction procedure is apparantly
strongly matrix dependent, ranging from 26% in tap water
to only 3–4% in waste water. Considering these aspects
and the overall complexity of the whole procedure, it is
doubtful whether this method can easily be applied to the
routine analysis of epichlorohydrin in samples of different
type and origin.
Efforts made in our laboratory to substantially simplify
the above described procedure by using a static headspace
technique achieved little success. The same holds true for
methods using liquid-liquid extraction which suffer from
poor recovery rates and tedious manual procedures. On
the other hand, the extractability of epichlorohydrin from
water by lipophilic media is indicating that other extrac-
tion techniques like solid phase extraction (SPE) may also
be used. SPE has some advantages over liquid-liquid par-
titioning. First of all it can be completely automated, avoid-
ing many steps of manual work. Additionally, higher en-
richment factors can be achieved more easily than by liq-
uid-liquid partitioning. We therefore have tried to develop
a method for the routine analysis of epichlorohydrin in
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water samples using solid phase extraction (SPE) for the lyze epichlorohydrin by injecting an aqueous solution directly into
enrichment of the analyte. The procedure is described below. the GC injector at 200° C without any significant hydrolytic de-
2 Experimental
2.1 Solid phase extraction
At present, cartridges filled with reversed-phase material are most
commonly used as solid phase adsorbent but our experiments
showed that this type of adsorbent gives essentially no recovery of
epichlorohydrin from water. It is well known that for the extraction
of more polar analytes resin adsorbents on the basis of styrene-di-
vinylbenzene copolymers (e.g. XAD®) are much better suited than
reversed-phase adsorbents. Cartridges filled with such resins have
been made commercially available recently. It turned out that they
show excellent recovery rates for epichlorohydrin.
2.1.1 Sample preparation procedure. Epichlorohydrin was supplied
by Aldrich (Nr. E 105-5) with a purity of 99% determined by GC.
Solid phase extraction cartridges (trade name: SDB-1) containing
200 mg of resin adsorbent were supplied by J.T. Baker, Phillips-
burg USA. After preconditioning successively with 3 mL acetone,
3 mL methanol and 3 mL distilled water, 100 mL of the water sam-
ple was pumped at a rate of 5 mL/min over the cartridge using an
AutoTrace™ SPE workstation (Zymark, Hopkinton USA). After
the sample had passed the cartridge, most of the remaining water
was removed by a stream of nitrogen (20 mL/min, 5 min) followed
by an elution step with 2 mL diisopropylether. For the following
determination by gas liquid chromatography the extract was trans-
ferred to a 2 mL GC sampler vial and a defined amount of 2-
chloropropionic acid-ethylester in diisopropylether was added as
an internal standard to characterize the total volume of the extract.
The procedure described above has been optimized with re-
spect to sample and eluent volumes. A sample volume of 100 mL
must not be exceeded in order to prevent a breakthrough of epi-
chlorohydrin. The elution step requires at least 2 mL of solvent,
otherwise substantial losses of epichlorohydrin are observed. The
remaining water content of the cartridge seems not to be a critical
point if it is not dryed extensively. It was found that a remaining
amount of 40–60 mg water, which can easily be determined by dif-
ferential weighing, does not influence the recovery of epichlorohy-
drin, whereas losses are observed after excessive drying. The wa-
ter remaining in the diisopropylether does not affect the determi-
nation by GC, making it unnecessary to dry the extract before GC
analysis. We even made the experience that it is possible to ana-
Fig. 1 GC-ECD calibration
curve for epichlorohydrin dis-
solved in diisopropylether.
Data points correspond to con-
centrations of 2.5, 5, 10, 20,
30, 50, 70 and 100 µg/L
composition of the compound.
2.2 Gas chromatography
Epichlorohydrin from a chromatographic point of view is a weakly
polar compound and causes no problems in gas chromatographic
systems which would impose special requirements for the type of
column or stationary phase. In real samples it may be advanta-
geous to shift the epichlorohydrin peak to higher k′-values in order
to improve the separation from other non-polar compounds con-
tained in the sample. Therefore, capillary columns with a polyeth-
yleneglycol stationary phase (Carbowax®) were used in this study.
Besides the FID and MS, the ECD can be used as GC-detector.
Using a solvent volume of 1 µL and a split ratio of 10 :1, the re-
sponses of these detectors for epichlorohydrin are quite different
and range from an absolute detection limit of 1 ng for the FID and
about 0.1 ng for the MS in single ion detection mode (m/e: 31, 57,
62) down to 2.5 pg for the ECD. The low detection limit achieved
with the ECD is somewhat surprising if compared with other
mono-chloro compounds and can only be explained by the specific
molecular structure of epichlorohydrin.
In this study a Hewlett Packard 5880 gas chromatograph
equipped with an HP 7673A autosampler, split/splitless injector,
FID and ECD (8 mCi 63Ni) was used. The carrier gas flow was 2
mL/min helium. The injector was set to 200° C and a split ratio of
1:10, the split valve beeing closed during injection for 0.5 min.
The detector was held at 250° C and purged with 20 mL/min ni-
trogen as make-up gas. For optimized separation of real samples
including waste water, the following temperature program was ap-
plied: injection at 20°C for 2 min; ramp rate 1: 10°C/min to 85°C;
ramp rate 2: 5° C/min to 150° C; ramp rate 3: 20° C/min to 200° C.
Under these conditions the epichlorohydrin peak eluted at about
5.2 min. The column was a 30 m × 0.25 mm DB-WAX fused sil-
ica capillary coated with a cross-linked film of polyethyleneglycol
of 0.5 µm thickness supplied by J & W Scientific, Folsom USA.
The injected sample volume was 1 µL.
3 Results
Using the above described conditions, gas chromatogra-
phy with electron capture detection of epichlorohydrin so-
lutions in diisopropylether shows an excellent linearity