War. Res. Vo|. 30, No. 3, pp.

644-648, 1996
Pergamon Copyright © 1996 ElsevierScienceLtd
0043-1354(95)00230-8 Printed in Great Britain. All rights reserved
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BIOLOGICAL TREATMENT OF WASTE WATER

CONTAINING GLYCOLS FROM DE-ICING AGENTS
L. N I T S C H K E *@, H. W A G N E R , G. M E T Z N E R , A. W l L K and L, H U B E R @
Bavarian State Bureau for Water Resource Management, Institute for Water Research,
Kaulbachstr. 37, D-80539, Munich, Germany

(First received February 1995; accepted in revised .form October 1995)

Abstract--Large amounts of de-icing agents consisting mainly of diethylene glycol and propylene glycol
are used at many airports during the winter time. At modem airports a large proportion of the mixture
of de-icing agents and meltwater is recycled and reused. Meltwater containing smaller amounts of de-icing
agents is usually collected in retention basins and discharged into municipal sewage treatment plants.
Extensive investigations have proved that waste water containing diethylene glycol may cause severe
disturbances in sewage treatment. Only by avoiding shock loads and by maintaining an adapted activated
sludge at the sewage treatment plant especially at a low waste water temperature can ensure that COD
and BOD effluent values do not exceed critical limits.

Key words---waste water treatment, de-icing agents, shock load, glycol.

INTRODUCTION It was reported that the way of biodegradation of

Large amounts of de-icing agents consisting mainly
of glycols are used at many modern airports during
winter. In general two types of de-icing procedures at
airports can be distinguished:
• de-icing of runways, parking areas etc.
• de-icing of aircrafts.
At a recently built G e r m a n airport propylene
glycol (PG) is used for runway de-icing. By contrast
a de-icing agent consisting mainly of diethylene glycol
(DEG) is used for aircraft de-icing. Aircraft de-icing
is generally based on an environmentally friendly
concept (Fig. 1). The mixture of de-icing agent and
meltwater that drips off the aircraft and contains
more than 5% D E G is recycled via destillation and
reused. Meltwater containing smaller amounts of
diethylene glycol is collected together with the
mixture of propylene glycol and meltwater from
runway de-icing in a retention basin and discharged
into a municipal sewage treatment plant with
biological purification including full nitrification and
correspondingly high sludge age. Especially during
intense de-icing periods disturbances in the sewage
treatment may be observed. Therefore the influence
of glycol de-icing agents on the sewage treatment
process was investigated by a research project
described here.
The biodegradation of oligo- and polyglycols was
described in the literature in particular by Swisher
(1970), Cox (1978), and Schrberl (1983, 1985, 1986).
*Author to whom all correspondence should be addressed.
diethylene glycol differs from that of other glycols.
Investigations into various sewage treatment plants
show that D E G was either almost completely or not
at all biodegradable i.e. only special species of
bacteria are able to use D E G in their metabolism. It is
supposed that the possession of a D E G hydrogenase
is responsible for the biodegradation of DEG. This
would explain the fact that a mixed activated sludge
population will reduce D E G in waste water either
considerably or not at all.
EXPERIMENTAL
Determination of BOD
The BOD~ of four different de-icing agents was measured.
The chemical compositions of these de-icing agents were:
• 35% DEG, 20% PG, 3% inhibitors and thickener, 42%
water
• 88% DEG, 2% PG, 1% inhibitor, 9% water
• 50% PG, 1% inhibitor, 49% water
• 75% PG, 5% urea, 1% inhibitor, 19% water
In addition a possible inhibition of the biodegradation of
the easily biodegradable peptone by a de-icing agent was
tested. All experiments were carried out with three different
concentrations of the de-icing agents. The test solutions
contained 50, 100, and 200 mg 1-' glycols, resp., at the
beginning of the tests. The temperature was maintained at
20°C and in a second experiment at 9°C in order to simulate
winter conditions.
Investigations with laboratory activated sludge plants
Laboratory activated sludge plants according to the
German standard DIN 38412-L26 were used to simulate the
water treatment conditions at the municipal sewage
treatment plant as exactly as possible. Instead of domestic
waste water a synthetic waste water was used as a basic

644
 Treatment of waste water containing de.icing agents 645

RUNWAY DE-ICING AIRCRAFT DE-ICING Finally the amount of the de-icing agent was increased to
75%.
propylene glycol (PG) diethylene glycol (DEG) (c) The laboratory activated sludge plants were fed with
synthetic waste water containing 400 mg 1 ~ COD for the
simulation of shock loads. A de-icing agent containing
1000 mg 1-~ COD was added to the influent of the plants
under shock load conditions after two weeks. These
experiments were repeated at 8°C.
>5%
Investigations at the airport and the municipal sewage
treatment plant during the de-icing period
24-h composite samples from the retention basin, the
influent to the biological sewage treatment, and the effluent
retention basin of the municipal sewage treatment plant were collected
during winter 1993/94. The COD of the samples was
determined. The content of DEG and PG was measured by
municipal sewage treatment plant
high performance liquid chromatography (HPLC). The
Fig. 1. Simplified scheme of waste water treatment for procedure is described in the caption for Fig. 3.
de-icing agents at an airport.
RESULTS AND DISCUSSION
nutrient solution (Table 1), to which different amounts of The results of the 5-d B O D tests indicated that
the de-icing agent were added.
de-icing agents containing mainly P G are better
As the experimental conditions should correspond largely
to the reality the ratio between synthetic waste water and biodegradable than products consisting mainly of
testing material (relating to the COD) varied at a constant D E G . It was shown in the experiments that at 9°C
BOD sludge loading. In several experiments the BOD sludge one of the de-icing agents containing 88% D E G did
loading varied as well as the COD of the basic substrate. inhibit the biodegradation of the easily biodegradable
The design of the laboratory activated sludge units and the
experimental conditions used in the experiments are given in peptone.
Table 2. The addition of de-icing agents to the basic
The waste water temperature was maintained at 16-18°C substrate (200 mg 1-~ C O D ) of the influent of the
except for some shock load experiments described below. laboratory activated sludge plants stepwise up to a
Generally, each test was running in parallel units. total C O D of 1200 mg 1-l (that means increasing
Altogether the following experiments were carried out: parts of glycol from 0 to 83%) shows at a
(a) Two laboratory activated sludge units were fed with temperature of 18°C a sufficient biodegradation of all
synthetic waste water containing 200 mg 1-~ COD. An tested de-icing agents. The C O D values in the
incremental load of a de-icing agent corresponding to 200, effluents ranged between 20 and 40 mg 1-~. Because
400, 600 up to 1000 mg 1-~ COD was added stepwise in each
case after two weeks, i.e. the sludge loading increased of the increasing B O D sludge loading the rate of
gradually from 0.1 to 0.6 gBOD5 (gMLSS) -~ d -~ (COD: nitrification was reported to decrease. Nevertheless
BOD5 ratio was supposed to be 2.0) at a constant waste the ammonia concentration did not increase. It was
water in-flow of 12 1 d-k The condition for nitrification was observed, that a higher organic load by the glycols
exceeded.
causes a higher sludge production. More nitrogen is
(b) Four laboratory activated sludge plants were run with
a sludge loading of about 0.15 gBOD5 (gMLSS)-~ d- J incorporated by the biomass.
under conditions for nitrification. Two plants at a time were Only of a de-icing agent containing 88% D E G
fed with a constant total COD of 800 mg 1-~ and caused a worse degradation for a short time after
1600 mg i -~, resp. At the beginning of these tests the total having increased its concentration. But within a few
COD of the irdluents consisted of 100% synthetic waste
water. After two weeks the influents were changed to days the degradation of this de-icing agent was also
75% synthetic waste water and 25% de-icing agent (relating nearly total.
to the COD). One week later the influents were changed The results of the other series of experiments
to 50% synthetic waste water and de-icing agent each. with a constant sludge loading of about 0.15 gBOD5
(gMLSS) -~ d -~ were similar. During a period of
Table 1. Composition of the used basic substrates (without de-icing 8 weeks a very good degradation of all the de-icing
agent) (data in mg 1-~) agents was obtained ( > 9 8 % ) . The nitrification was
COD nearly total with an ammonia concentration of
150 <0.5 mg 1-I in the effluent.
Ingredient (resp. DIN 38412-L26) 200 400 In addition to these observations special shock
Peptone 80 110 220 load experiments were carried out. F o u r laboratory
Meat extract 55 76 152 activated sludge plants were fed with synthetic waste
Urea 15 21 42
NaCI 3.5 4.8 9.6 water containing 400 mg 1-I C O D for one week. Two
K2HPO4 14 19.3 38.6 plants contained activated sludge which was adapted
NaCO3 98 135 270 to the biodegradation of glycols from previous
Tap water ad 1000ml ad 1000ml ad 1000ml
DOC 60 80 160 experiments. The other two plants were filled with
BODs 75 100 200 ordinary activated sludge of a municipal sewage
N 20 28 56
treatment plant, which was not adapted to the
646 L. N i t s c h k e et al.

Table 2. Design and operation of the laboratory activated sludge units

Aeration chamber volume 1 3
Clarifler volume 1 1.5
MLSS g 1-~ 4
Return sludge flow % 100
In-flow 1 d -t 12 4.5 2.25
Hydraulic retention time h 6 16 32
COD mg 1 L 200 400 600 800 1200 800 1600
BOD~ mg 1-~ 100 200 300 400 600 400 800
Sludge loading gBOD5 (gMLSS) -~ d -j 0.1 0.2 0.3 0.4 0.6 0.15 0.15
Parts of de-icing agent % 0 50 67 75 83 25-75 25-75
(related to COD)

biodegradation of glycols. One week after starting the
tests a de-icing agent containing mainly DEG was
continuously added to the synthetic sewage influent
of the plants. The concentration of the de-icing fluid
added was equivalent to 1000 mg 1-1 COD. As to be
expected the COD of the effluents of the plants rose
immediately (Fig. 2). However, the increase in COD
of the effluents of plants filled with adapted activated
sludge was considerably lower compared with the
effluents of plants filled with not adapted activated
sludge. In addition the COD values normalized
within a shorter time.
Figure 3 shows the HPLC chromatograms of the
influent and the effluent of a laboratory activated
sludge plant. The de-icing agent added contained
35% propylene glycol and 20% diethylene glycol.
The samples were collected two days after starting
shock load conditions. The PG removal was
calculated to 97%, DEG removal to only 83%. Four
days after starting this test the DEG removal
increased to 93% and after 7 d to 96%. PG was not
detectable in the effluent from the fourth day after
starting the test. It can be shown that DEG is
considerably less biodegradable than PG.
Thus, essential effects of additional glycol load
were only measured under shock load conditions.
Therefore only these experiments were repeated at
COO [mg/I]
25O
200
150
100
50
0 activated sludge adapted to the glycols.
I 2 3 4
time [days]
-t- not adapted sludge -~- adapted sludge
Fig. 2. C O D c o n c e n t r a t i o n o f a n effluent o f a l a b o r a t o r y
activated sludge plant after the beginning of a shock load
with 1000 mg 1-I COD by a de-icing agent (88% DEG, 2%
PG): 16-18°C, 400 mg 1-t COD by nutrient solution,
4 g 1-~ suspended solids; 0.2 gBODs (gMLSS)-t d -j load
before the beginning of the shock load.
lower temperatures, because it was expected that
these effects are even stronger at low waste water
temperatures.
A temperature of 8°C was adjusted in four
laboratory active sludge units to simulate waste water
temperatures in winter. After 18 d the temperature
was increased to 12°C (Fig. 4). The shock load
experiments at these temperatures were carried out in
the same way as the investigations at normal
temperatures described above. Testing de-icing
agents containing mainly PG it was found that the
COD of the effluent hardly increased after starting
the shock load conditions. In contrast to this the
shock load experiments of de-icing agents containing
mainly DEG showed a drastic decrease of the degree
of COD elimination.
Figure 4 shows the results of another experiment.
A de-icing agent (88% DEG, 2% PG) was added to
the basic load of synthetic waste water. The final
de-icing agent concentration which was attained in a
period of 3 d was equivalent to 900 mg 1-1 COD. The
degree of elimination decreased rapidly after the
de-icing agent had been added. Additionally, the
biodegradation of the synthetic waste water was
inhibited after the addition of the de-icing agent. By
raising the temperature to 12°C the degree of
elimination only slightly improved.
The results of the tests in the laboratory activated
sludge plants were to be put into practice in winter
1993/94. The indispensable adaption of the activated
sludge of the municipal waste water treatment plant
to DEG was achieved by a gradually increasing load
of waste water containing DEG from the retention
basin. Shock loads had to be avoided. Furthermore,
the retention basin had not to be emptied fast and
completely during periods of no de-icing activities at
the airport. Waste water containing glycols had to be
discharged into the municipal sewage treatment plant
in a space of time as long as possible to maintain the
5 6 7
At least twice a week 24-h composite samples from
the retention basin, the influent to the biological
sewage treatment and the effluent of the municipal
sewage treatment plant were collected during winter
1993/94. The COD and the concentrations of DEG
and PG were determined. Figure 5 shows the
concentration of COD and DEG in the effluent of the
sewage treatment plant and the air temperature
 Treatment of waste water containing de-icing agents 647

10

PG

!
DEG

>E 4
\ \
Influent
_ I ~

Effluent

-1 t i i i i
0.11 1 2 3 4

Min
Fig. 3. HPLC chromatogram of an influent and an effluent of a laboratory activated sludge plant two
days after the beginning of the shock load. HPLC conditions: (column) Hypersil ODS (250 x 4.6 mm,
5 pm); (eluent) 100% water, 2 ml min-'; (detection) refractive index.

during a cold period in February 1994. As shown in treatment plants. The discharge of waste water
the diagram D E G was detectable and COD shortly containing DEG into a municipal sewage treatment
increased during this period. These observations fully plant may lead---especially in case of shock loads and
confirmed the results obtained by laboratory at a low waste water temperature--to a drastic
activated sludge plants. decrease of the degree of COD removal. To maintain
a sufficient degree of biodegradation it is necessary to
adapt the activated sludge to DEG during a several
CONCLUSION
days' adaption period. Shock loads have to be
Waste water from aircraft de-icing containing avoided. The activated sludge has to be maintained
DEG may cause severe disturbances in sewage in its adapted state to glycols as long as possible

COD [rag/I] DEG a n d C O D in the STP effluent [mg/I] temp. [°C]

1.400 60 / [

1.200, ¢.n~ ~! 10

1.000 / ,
~- ~ , ~. ~-K~ ~
800 )~" •'.. i~ ~, ,/ ,~,, ~." =5
'y' .×'
L
30
6oo | -.. ~- -~
20 ~ - . "-=". - ~' . .." i
400 ~ ~ ]o
•. , !

0 0 • ~ .... 5
0 2 4 6 8 10 12 14 16 18 20 2 4 6 8 10 12 14 16 18 20 22 24 26
days February 1994

[ ] effluent [ ] i n f l u e n t ($yn.sawage) [ ] intl. (de-icing agent) + DEG - - COD ~- air temp.

Fig. 4. Example of the COD after the beginning of a shock Fig. 5. DEG and COD of the effluent of a de-icing agents
load by a de-icing agent (88% DEG, 2% PG) at low waste waste water treatment plant in February 1994 (STP--
water temperature, sewage treatment plant).
648 L. Nitschke et al.
during periods of no de-icing at the airport, i.e. the
discharge of the retention basin should be stretched
as long as possible.
REFERENCES
Cox D. P. (1978) The biodegradation of polyethylene
glycols. Adv. Appl. MicrobioL 23, 173-194.
Sch6berl P. (1983) Polyethylenglykolketten-Metabolismus
durch Pseudomonasfluorescens, Stamm P 200 am Beispiel
des Triethylenglykols (Triethylene glycol as an example of
the metabolism of polyethylene glycol chains by
Pseudomonas fluorescens, strain P 200). Tenside Deter-
gents 20, 57-65.
Sch6berl P. (1985) Der Metabolismus von Monoethylen-
bzw. Diethylenglykol durch Corynebacterium spec.
Stamm E bzw. Pseudomonas fluorescens Stamm P 201
(The metabolism of mono- and diethylene glycol by
Corynebacterium spec. strain E and Pseudomonas
fluorescens strain P 201, resp.). Tenside Detergents 22,
70-77.
Sch6berl P. (1986) Kata- und Metabolismus von Oli-
goethylenglykol (Cata- and metabolism of oligoethylene
glycol). Tenside Detergents 23, 255-266.
Swisher R. D. (1970) Surfactant Biodegradation, Surfactant
Science Series, Vol. 3. Marcel Dekker, New York.