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@PHDTHESIS{Linnemann:37446,
author = {Linnemann, Volker},
title = {{U}mweltverhalten von {MTBE} nach
{G}rundwasserkontamination},
volume = {40},
school = {Universität Bonn},
type = {Dr. (Univ.)},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {PreJuSER-37446},
isbn = {3-89336-339-4},
series = {Schriften des Forschungszentrums Jülich. Reihe Umwelt /
Environment},
year = {2003},
note = {Record converted from VDB: 12.11.2012; Universität Bonn,
Diss., 2002},
abstract = {Since the late seventies, methyl-tert-butyl ether (MTBE)
has become one of the mort widely produced chemicals in
Europe and the USA due to its use as a fuel additive. MTBE
was first used as a substitute for the environmental poison
tetraethyl lead because of its anti-knock properties.
Statutory requirements for minimum volumes of
oxygen-containing additives in motor fuels, to protect the
atmosphere against the cl imate-relevant trace gases carbon
monoxide (CO) and ozone (Os), greatly increased the demand
for MTBE in the USA. One consequence was an increasing
number of groundwater and soil contaminations as well as
complaints of damage to health associated with MTBE. Since
the air had been kept clean at the expense of the
groundwater and the soil, the use of MTBE is prohibited in
the USA after 2003. In Europe increased numbers of
MTBE-contaminations in the groundwater and surface waters
have been reported. Goal of this PhD thesis was the
investigation of the MTBE mass transport into the atmosphere
after a contamination of the groundwater. For this studies a
tripartite experimental concept was selected: First of all,
a soil column experimental setup for studying mass transport
in undisturbed soil monoliths was designed, constructed and
validated. With this facility it was possible to create
under defined and reproducible experimental conditions an
aquifer below the soilcore, variable in height, in which a
contamination with MTBE had been simulated in a real
concentration range of 100 to 200 mg L$^{-1}$. A stream of
air flowed over the soil surface through the artificial
atmosphere, and was collected and analysed with respect to
the composition of volatile organic chemicals. Adsorption
onto multibed solid adsorbent material with subsequent
thermodesorption GC/MS analysis was developed for air
collection and displayed good sampling performance with
excellent detection limits. The groundwater samples were
analysed by radioactivity-HPLC, -GPC or a new direct
injection- GC/MS analytical technique. For this
liquid-injection-methods the detection limit still has to be
improved. In the first experiment, up to 47 ppb (170 ng
m$^{-3}$) of MTBE was detected in the air. MTBE was not
continuously recovered in the air but only occurred in
pulses. Maximum values were measured, in particular, in the
first few days. The mass transfer rates through the soil
into the atmosphere were in the region of 1.94 ± 1.88
$\mu$g m$^{-2}$ h$^{-1}$ in the first experiment with an
equilibrium value of approx . 0.45 ± 0.02 $\mu$g m$^{-2}$
h$^{-1}$. In the second experiment with
[$\alpha$,$\alpha$'-$^{14}$M] MTBE, only low volatilization
was measurable. At the same time, the water balance in the
experimental System was also recorded, which enabled a
qualitative relation to the MTBE loss to be established. The
simulated aquifer was redesigned for a scale-up experiment
and also the air sampler adapted for volatile hydrocarbons
at the fieldlike wind tunnel with a lysimeter. The new
sampling unit was validated in several preliminary
experiments and displayed good collecting efficiency for the
high volume flows applied. Analogously to the second column
experiment, over an experimental period of 4 weeks hardly
any mass transport of MTBE through the soil was determined.
The recovery rate in both experiments with $^{14}$C-MTBE was
in the region of 83 to 102 \% of the applied radioactivity
(AR). As described in the literature only slight adsorption
to the soil particles was found for MTBE. Since the soil
columns and the lysimeter represented a compartment of the
ecosystem with functioning microflora, the microbial aerobic
degradation in the soil was determined in two laboratory
studies. A maximum mineralization of 1.6 \% AR was detected
as a function of the previous contaminations of the soil and
the soil type. Moreover, rapid volatilization of the MTBE
from the surface took place perceptibly reducing the
bioavailability . The results obtained were readily
applicable to the transport studies.},
cin = {ICG-IV},
ddc = {333.7},
cid = {I:(DE-Juel1)VDB50},
pnm = {Chemie und Dynamik der Geo-Biosphäre},
pid = {G:(DE-Juel1)FUEK257},
typ = {PUB:(DE-HGF)11 / PUB:(DE-HGF)3},
url = {https://juser.fz-juelich.de/record/37446},
}