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Abstract
In a series of experiments with soil samples of contaminated sites we investigated the effect of special surfactant
combinations and other additives on the kinetics and extent of solubilization and degradation of PAH. Biodegrada-
tion tests showed a positive effect of adding surfactant combinations T10 and T15. The effect was more pronounced
when samples exhibited low degradation effectivity without surfactants. Addition of surfactants counterbalanced the
dependence of bioavailability of the individual PAH compounds on their solubility in pure water. Changing the
composition of surfactant combinations different tendencies were observed for the extent of solubilization and
degradation, i.e. very high concentrations of PAH in the liquid phase may have toxic effects on the soil microflora.
However, addition of a sorbent had the most remarkable effect on residual pyrene concentration in a sandy soil,
whereby the contamination was transferred to the sorbent phase. Sorption to the sorptive phase and solubilization are
substantially faster processes than degradation. © 2000 Elsevier Science B.V. All rights reserved.
0927-7757/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 9 9 ) 0 0 2 1 7 - 4
2 T. Sobisch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 162 (2000) 1–14
Fig. 2. Removal of individual PAH compounds as function of their original aqueous solubilities.
6 T. Sobisch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 162 (2000) 1–14
Fig. 3. Effect of composition of surfactant combinations on solubilization and removal of pyrene (sample D, 5 g/20 ml, 2%
surfactant per soil).
microflora is low, as in the case of sample A. As The solubilizing action of the surfactant combi-
could be expected with sample C, in the presence nations used is not solubilization in terms of
of mineral oils with appropriate bioavailability, ‘preparation of thermodynamically stable isotropic
surface active bioproducts may be released (see solutions of substances otherwise only slightly
below), which would have a positive effect on the soluble’ [8], i.e. micellar solubilization. Because of
physico-chemical and biological removal of PAH these surfactant combinations are only dispersed in
without addition of technical surfactants. the water phase, the PAH will partition between the
Bioavailability of individual PAH compounds is soil and the dispersed surfactant phase. Therefore,
related to their solubility in the aqueous phase. This the critical volume necessary for solubilization of
trend is also evident for the degradation tests with PAH of high molecular weight [9] may not be a
no surfactant added (Fig. 2). The percentage of the limiting factor, as in the case of micellar solubiliza-
individual compounds remaining in soil after treat- tion. It is obvious from Fig. 2 that addition of 1%
ment is depicted against their aqueous solubility T15/1 caused a reduced removal of PAH, whereas
(S). The literature data for the solubilities are addition of 0.1% was almost as effective as the
compiled from refs. [6,7]. Unreasonably high values amendment with 1% T10/1.
were excluded, which was also the case for the only
3.3. Effect of surfactant composition on the
available data for indeno(1,2,3-ed)pyrene (0.062
extent of solubilization and degradation of pyrene
mg/l [7]). The addition of 1% T10/1 or T15/1 to the
soil caused the fraction of the individual com- Fig. 3 shows the influence of the composition of
pounds remaining in soil to be nearly independent surfactant combinations on solubilization and
on their original aqueous solubilities for sample B. degradation for sample D, a subsample of sample
In the case of sample C with higher biological C with an initial pyrene concentration of 417
activity the dependence on the solubility values is mg/kg. The residual pyrene concentration in soil
more pronounced. The addition of T10/1 and and in the water phase was analyzed after one week
T15/1 weakens this tendency. shaking of the soil suspension (5 g/20 ml) amended
T. Sobisch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 162 (2000) 1–14 7
Fig. 4. Effect of surfactant concentration on solubilization and removal of pyrene (sample D, 7 days).
with nutrients and 2% surfactant per soil. Chang- During the slurry tests the fraction of pyrene
ing the quantity of the hydrophobic compound extractable after additional saponification re-
between 37 and 70% only a slight variation in mained on the low initial level. Hence biological
residual and solubilized amounts of pyrene was fixation of PAH might not have been occurred.
observable. With T15, were only the hydrophobic
component in T10 was changed (same hydrophilic 3.4. Influence of surfactant concentration on
compound), the solubilizing power decreased by solubilization and residual concentration of pyrene
more than 50%. Replacing the hydrophilic compo-
nent in T10 and T15 by a slightly more hydrophilic The degree of solubilization and concentration
surfactant, which differed only in the degree of of pyrene in soil (sample D) after one week shaking
ethoxylation (HLB: 0.5), solubilization was en- was measured as function of concentration of
hanced (T10 T36) or slightly reduced (T15 T15/2 (Fig. 4).
T35). On the other hand, if the hydrophilic As could be expected, the degree of solubiliza-
compound in T10 was substituted by a surfactant tion is increased with increasing surfactant concen-
of the same HLB value ( T16), the degree of tration. On the other hand the total residual pyrene
solubilization was reduced by an order of magni- content in the soil slurry (soil+ liquid phase) is
tude. lowest at a surfactant concentration of 0.5%.
Therefrom it is evident that the structure of the Lower surfactant concentrations (0.1–0.3%) ex-
hydrophilic compound has a marked influence on hibited a negative effect on residual concentration.
the solubilization effect of the formulation. Increasing the soil–water ratio to 5 g/10 ml the
Interestingly, the extent of biodegradation, de- degree of degradation as well as the fraction of
duced from the total of pyrene determined in soil pyrene solubilized from soil is enhanced. Enhanced
and solution, is the highest for the surfactant solubilization corresponds to higher ratios of PAH
combinations with low solubilizing power and vice in the liquid phase per surfactant added at
versa. This may be caused by the very high concen- concentrations of 0.5% T15/2. This might be due
tration of PAH in the liquid phase, which may to the formation of active bioproducts (biosurfac-
have had a toxic or inhibiting effect on the soil tants or biopolymers) released by the soil mi-
microflora. croflora, maybe preferentially during degradation
8 T. Sobisch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 162 (2000) 1–14
Fig. 5. Effect of different additives on solubilization and removal of pyrene (sample D, 5 g/10 ml, 7 days).
of the mineral oil contaminants. Release of such 3.5. Screening of effecti6ity of different additi6es
bioproducts is reflected by increased foaming, The performance of different surfactant combi-
which had been observed after a distinct period of nations and other additives (polymeric compounds
shaking. It seems that dilution of the soil microflora and sorbents) was further tested under standard
has an adverse effect on its overall activity, i.e. conditions, i.e. shaking over a period of 1 week, 5
biodegradation and production of active metabo- g soil (sample D)/10 ml. Selected results are com-
lites. Another indication of the production of active piled in Fig. 5.
metabolites is the enhanced solubility of pyrene in Compared with the sample not amended with
the soil slurries amended only with nutrients. In the additives (only with nutrients) addition of various
case of 5 g soil/20 ml the pyrene concentration in surfactant combinations caused only a further
the liquid phase reaches a value of 0.18 mg/l after reduction of the residual pyrene concentration in
one week, which is only slightly above the value for soil of about 10% (5 g/10 ml values). In the case
its solubility in pure water (0.13 mg/l), but a value of the formulation with high solubilization power
of 3.1 mg/l for 5 g soil/10 ml. After 2 weeks the T36/2 this could be reduced further by 10%, but
degradation was completely inhibited. Addition of
concentration of pyrene increases to a value of 0.9
0.1% of the polymeric compound Z18 reduced the
mg/l (5 g soil/20 ml). Enhanced mutual attrition of
amount of pyrene remaining in soil to 58% of the
soil grains may play also an important role in
initial value. When 0.1% Z18 and 0.5% T15/2 were
increasing the extent of solubilization if (technical added simultaneously a reduction to 52% was
or biological) surface active substances are present reached. In these cases the relatively high concen-
to stabilize mineral oils in suspension which will trations of pyrene in the liquid phase did not
carry PAH into the liquid phase. inhibited degradation.
T. Sobisch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 162 (2000) 1–14
Fig. 6. Effect of different additives on the kinetics of pyrene removal (sample D, 5 g/10 ml).
9
10 T. Sobisch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 162 (2000) 1–14
Fig. 7D. Kinetics of pyrene removal from sample D (5% SI + 0.1% Z18).
14 T. Sobisch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 162 (2000) 1–14
Addition of 5% of the sorbent S1 reduced con- in the liquid phase may have toxic effects on the
tamination of soil substantially. S1 was far more soil microflora.
effective than other sorbents tested, i.e. activated Addition of the sorbent S1 had the most re-
carbon or wood. Without further additives markable effect on residual pyrene concentration
present pyrene content of soil was lowered to in a sandy soil, whereby the contamination was
44%, when 41% of the initial amount of pyrene transferred to the sorbent phase. Sorption to the
was concentrated in the sorbent phase. With addi- sorbent and solubilization are substantially faster
tional 0.5% T15/2 or 0.1% Z18 these levels processes than degradation.
reached 36/44% (T15/2) and 34/43% (Z18). However, under no circumstances removal rates
and residual concentrations were in the order of
3.6. Kinetics of pyrene remo6al and solubilization values which would be necessary for a competitive
decontamination process. Therefore a new two
Fig. 6 shows the kinetics of pyrene removal stage bioreactor process was developed (patent
from sample D. Figs. 7A, 7B, 7C and 7D summa- pending, described elsewhere [10,11]), which en-
rize the variation of the pyrene fraction in soil and hances removal rates drastically.
the liquid phase or bound to the sorbent.
In the presence of 5% of sorbent S1 + 0.1% Z18 Acknowledgements
a fast removal of pyrene was observed. After a
few days the residual pyrene concentration ap- We gratefully acknowledge the support of the
proached 34% of the initial value. Correspond- Bundesministerium für Bildung, Forschung und
ingly, 43% of pyrene was concentrated in S1 (Fig. Technologie under grant number FKV 0211001J6
7D). In all other cases the pyrene concentration and FKV 0150402J6.
reduced only slowly with only a moderate positive
effect of adding 0.5% T15/2 or 0.1% Z18.
References
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[11] T. Sobisch, H. Niebelschütz, Contaminated Soil ‘98, Pro-
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were observed for the extent of solubilization and on Contaminated Soil, 17 – 21 May, Edinburgh, Thomas
degradation, i.e. very high concentrations of PAH Telford Publishing, Ltd., London, 1998, pp. 1189 –1190.