Trace Analysis of Organic Pollutants with GCMS according

to the new European Drinking Water regulation

M. Geißler, U. Potyka, H.-U. Baier
Shimadzu Deutschland GmbH, Duisburg, Germany

Introduction Parameter Limit (µg/l) Detection limit in

% of the limit
Precision in %
of the limit
Since the 1st of January 2003 the new European Acrylamide 0,1 - -
Benzo[a]pyrene 0,01 25 25
Drinking Water regulation is effective in Germany Benzene 1 25 25
(TVO 2001). Its aim is to protect human health 1,2-Dichloroethane
Epichlorhydrine
3
0,1
10
-
25
-
from the bad influences of contaminated drinking Pesticides (single 0,1 25 25
components)
water. All water that is used for the preparation Pesticides (Sum) 0,5 25 25
of food as well as for cleaning of material used PAH (4 components)
TRI / PER
0,1
10
25
10
25
25
for the preparation of food and water that is used Trihalomethanes 50 10 25
Vinylchloride 0,5 - -
for personal hygiene is regulated under the
European drinking water regulation. Water used
for these purposes should not contain chemical Independently of their toxicity for the pesticides
substances in concentrations that could cause in Drinking Water a limit of 0.1µg/l for single
harm to human health. For many compounds components is specified. The majority of
limits are defined that have to be controlled on a positive determinations is due to the presence of
regular basis and cannot be exceeded. the pesticides Atrazine and its major degradation
product Desethyl-Atrazine. Atrazine has been
Analysis of Organic Pollutants in Drinking Water used extensively especially in the cultivation of
The analysis of organic pollutants in drinking corn, but was also used for asparagus, potatoes
water is a complex task which requires a high Fig. 2: Calibration curve Dichloroethane and tomatoes. Atrazine is toxic for water
degree of precision, know-how and modern organisms but shows only little toxicity for
analytical equipment. The analysis technique also for the single components to be determined humans. Its deterioration in the environment is
used has to be able to detect a large array of are given in Table 1. In this study the analysis of relatively slow. Atrazine and Desethyl-Atrazine
compounds in very low concentrations according VOC´s including Benzene and Pesticides was have been analysed in this study, showing that
to the specified limits. For the organic pollutants studied with GCMS. the requirements
a detection limit of 25 % or 10 % (for chlorinated of the Drinking
organic compounds) has to be achieved. The VOC Analysis by Headspace GCMS Water regulation
precision of the results shall not be more than Many VOC´s are toxic and some of them are also could be fulfilled.
25 % of the limit. cancerogenic. They are soluble in fat and thus can
accumulate in the natural cycles. For the analysis In Fig. 3 the
of VOC´s the Headspace technique is employed. calibration curve
In Figure 1 a chromatogram of the VOC 1,2 for Atrazine in a
Dichloroethane in a concentration of 1 µg/l is concentration
shown giving a signal/noise of 65:1. Fig. 2 shows range of 0.015 to
the calibration curve in the concentration range of 1.5 µg/l is shown.
0.1 to 10 µg/l (correlation coefficient 0.9997). All Fig. 4 and 5 show
data were acquired in SIM mode. The limit in the the determination
drinking water regulation is 3 ng/l, so the of Atrazine and
requirements are easily met. Desethyl-Atrazine
in a real sample.
Benzene is one of the most prominent aromatic Table 2 shows Fig. 4: Chromatogram
hydrocarbons and next to the PAH one of the most the data for the Atrazine (real sample)
important environmental carcinogens. It is emitted concentration and
mostly from fuel used in cars. In the new drinking standard
water regulation benzene has to be determined as deviation of the 3
a single parameter in a concentration of 1 µg/l. replicates. For
Also for the analysis of benzene the headspace Atrazine a very
Fig. 1: Chromatogram Dichloroethane GCMS technique is used. good repro-
ducibility can be
GCMS Analysis of Drinking Water Analysis of Pesticides achieved but for
The coupling of gas chromatography with mass In modern agriculture still a large number of Desethyl-Atrazine
spectrometry is a powerful tool for the qualitative pesticides is commonly employed. Generally the standard
and quantitative analysis of drinking water pesticides are considered as harmful to human deviation is
samples. Due to its high sensitivity it fully health. They can cause malfunctions of kidney and higher. This is
complies to the regulations of the drinking water liver and some of them are also cancerogenic. due to the high
directive. In scan mode organic pollutants can be polarity of the
identified even in low concentrations compound which
unambiguously by library search in commercially leads to a tailing
available spectral libraries like NIST or Wiley and of the peak. A
special libraries like the Shimadzu Pesticides column with high Fig. 5: Chromatogram
library which includes EI and also NCI (Negative polarity would be Desethyl-Atrazine (real sample)
Chemical Ionisation) spectra. NCI measurements preferable for this
give high sensitivity for compounds with high compound, however a 5 % phenyl substituted
electronegativity like e.g. chlorinated substances. methyl polysiloxane column was chosen for the
Measurements in SIM mode (Single Ion analysis since a wide range of compounds can be
Monitoring) enhance the selectivity and increase analysed on this column in one run.
the sensitivity of detection.
Triazine MW (µg/l) STD (µg/l) STD (%)
Atrazine 0,121 0,002 1,7
Classification of Organic Pollutants Desethyl-Atrazine 0,292 0,013 4,4
Substances which have to be analysed
according to the drinking water regulation can be Instrumentation
classified into the following groups: volatile GCMS-QP2010
(chlorinated) organic hydrocarbons (VOC), GCMSsolution software
polycyclic aromatic hydrocarbons (PAH) and AOC-5000 autosampler
pesticides. The limits for the different groups and Fig. 3: Calibration curve Atrazine Shimadzu Pesticide EI/NCI library

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