Bioavailability of polycyclic aromatic hydrocarbons in soils and sediments

171 Pages·2012·5.86 MB·English

r" '?n >
STELLINGEN
1. Extracties met organische oplosmiddelen en waterige oplossingen van surfactants zijn
ongeschikt voor het voorspellen van de biobeschikbaarheid van hydrofobe organische
verontreinigingen in bodems en sedimenten.
Dit proefschrift
Chung, N.; Alexander, M. Environ. Sci. Technol. 1998, 32, 855-860
2. De verregaande acceptatie van modellen die de bodem-organische-stof beschrijven als een
samenraapsel van discrete amorfe en gecondenseerde domeinen (amorphous/condensed,
rubbery/glassy, soft/hard) is verbazingwekkend, gezien de minieme hoeveelheid onderzoek
die is gedaan naar het daadwerkelijk bestaan, de chemische samenstelling en de fysische
conformatie van dergelijke domeinen.
Dit proefschrift
3. Het gebruik van radiaal-diffusiemodellen voor het beschrijven van de desorptie van
hydrofobe organische verontreinigingen in bodem- en sedimentsystemen wekt ten onrechte
de indruk dat men deze systemen goed genoeg kent om de keuze voor dergelijke
mechanistische modellen te rechtvaardigen.
4. Een van de saneringsdoelstellingen die is geformuleerd in het kader van het
Uitvoeringsprogramma Beleidsvernieuwing Bodemsanering is het bereiken van een stabiele
eindsituatie in de ondergrond binnen 30 jaar na start van de sanering. Deze soepele
doelstelling zou het gebruik van extensieve saneringstechnieken in de hand moeten werken.
Helaas is het momenteel nog niet mogelijk om bij de selectie van een saneringsvariant een
goed gefundeerde voorspelling te doen over het al dan niet halen van bovenstaande
doelstelling met behulp van extensieve saneringstechnieken.
Kooper, W. (Quintens advies & management) Van trechter naar zeef: Afwegingsproces
saneringsdoelstelling Sdu Uitgevers: Den Haag, 1990
5. Het driedimensionale humuszuurmodel dat is beschreven door Schulten is niet correct omdat
de samenstelling van het humuszuur deels is gebaseerd op onjuist gei'nterpreteerde
pyrolysedata. Deze onjuiste interpretatie had kunnen worden voorkomen door het in acht
nemen van de "pitfalls in analytical pyrolysis" beschreven door Saiz-Jimenez.
Schulten, H.-R. FreseniusJ. Anal. Chem. 1995, 351, 62-73
Schulten, H.-R.; Schnitzer, M. Soil Sci. 1997, 162, 115-130
Saiz-Jimenez, C. Environ. Sci. Technol. 1994, 28, 1773-1779
6. Het is in veel gevallen efficienter het geheugen van een systeembeheerder uit te breiden dan
het geheugen van elke afzonderlijke computer onder zijn of haar beheer.
7. Het veel gehoorde excuus dat men een mobiele telefoon heeft om bereikbaar te zijn, is
tegelijk het beste excuus om het ding zo min mogelijk te gebruiken.
Stellingen behorende bij het proefschrift "Bioavailability of Polycyclic Aromatic Hydrocarbons
in Soils and Sediments: Prediction of Bioavailability and Characterization of Organic Matter
Domains"
Chiel Cuypers
Wageningen, 6 juli 2001
Bioavailability of Polycyclic Aromatic Hydrocarbons in
Soils and Sediments:
Prediction of Bioavailability and Characterization of Organic Matter Domains
Chiel Cuypers
PROMOTOR
prof. dr. ir. W.H. Rulkens
hoogleraar in de milieutechnologie
CO-PROMOTOR
dr. ir. J.T.C. Grotenhuis
universitair docent bij de sectie Milieutechnologie
SAMENSTELLING PROMOTIECOMMISSIE
prof. dr. W.H. van Riemsdijk Wageningen Universiteit
prof. dr. H.J.P. Eijsackers Vrije Universiteit, Amsterdam
prof. dr. G. Malina Technical University of Czestochowa, Poland
dr. P.C.M. van Noort RIZA, Lelystad
dr. ir. H.H.M. Rijnaarts TNO-MEP, Apeldoorn
ff7n ! "X~5 6> '<'*
Mf'4 0.-'?°
Bioavailability of Polycyclic Aromatic Hydrocarbons in
Soils and Sediments:
Prediction of Bioavailability and Characterization of Organic Matter Domains
Chiel Cuypers
PROEFSCHRIFT
ter verkrijging van de graad van doctor
op gezag van de rector magnificus
van Wageningen Universiteit,
prof. dr. ir. L. Speelman,
in het openbaar te verdedigen
op dinsdag 4 September 2001
des namiddags te half twee in de Aula
CIP-DATA KONINKLIJKE BIBLIOTHEEK, DEN HAAG
Author : Cuypers, C.
Title: Bioavailability of polycyclic aromatic hydrocarbons in soils and sediments:
Prediction of bioavailability and characterization of organic matter domains
ISBN: 90-5808-438-8
Publication year: 2001
Subject headings: PAH / bioavailability / soil / sediment / organic matter
Thesis Wageningen University, Wageningen, The Netherlands - With references - With summary in
Dutch- 161 p.
ABSTRACT
Cuypers, C. 2001. Bioavailability of polycyclic aromatic hydrocarbons in soils and sediments:
Prediction of bioavailability and characterization of organic matter domains. PhD-thesis,
Wageningen University, The Netherlands, 161 pages.
Polycyclic aromatic hydrocarbons (PAHs) constitute a group of priority pollutants which are of
increasing environmental concern because of their adverse effects on humans, animals, and
plants. Soils and sediments generally serve as a sink for PAHs, which leads to the accumulation
of PAHs at contaminated sites. In the last decade, bioremediation has been frequently used for
the clean-up of such contaminated sites. However, despite the common use and cost-
effectiveness of bioremediation, it is generally observed that a residual fraction remains
undegraded even when optimal biodegradation conditions have been provided. In many cases
the recalcitrance of this residual fraction is caused by a limited bioavailability of PAHs. The
present thesis focuses on the development of simple and rapid laboratory methods for the
prediction of PAH bioavailability. As an integrated part of this study, it was aimed to expand the
current knowledge on the structure of amorphous and condensed soil/sediment organic matter
(SOM) domains. It is believed that PAHs sorbed in amorphous domains are readily bioavailable,
while PAHs sorbed in condensed domains are poorly bioavailable.
Three different methods were investigated for the prediction of PAH bioavailability: persulfate
oxidation, cyclodextrin extraction, and surfactant extraction. Persulfate oxidation appeared to be
a good and rapid method for the prediction of PAH bioavailability. It was demonstrated that a 3
hour oxidation at 70 °C was sufficient for the removal of all bioavailable PAHs. The oxidation
method was successfully validated in a study with 14 historically contaminated soil and
sediment samples. Cyclodextrin extraction and surfactant extraction were investigated in a study
with two sediment samples, using hydroxypropyl-p-cyclodextrin and Triton X-100 (surfactant)
as model compounds. It was demonstrated that hydroxypropyl-p-cyclodextrin extracted
primarily readily bioavailable PAHs, while Triton X-100 extracted both readily and poorly
bioavailable PAHs. Moreover, hydroxypropyl-P-cyclodextrin did not affect the biodegradation
of PAHs, while Triton X-100 enhanced the degradation of low molecular weight PAHs.
Altogether, it may be concluded that persulfate oxidation currently provides the most rapid
validated method for the prediction of PAH bioavailability in soils and sediments.
To study the composition of amorphous and condensed SOM domains, two different approaches
were followed: (i) samples were subjected to persulfate oxidation to remove amorphous SOM,
before and after which the composition of SOM was studied by thermogravimetric analysis,
pyrolysis-GC/MS, and CPMAS 13C-NMR; (if) samples were split in two parts, one part was
bioremediated to remove bioavailable PAHs, and both the bioremediated and non-bioremediated
part were subjected to 9 different chemical treatments with a known effect on SOM structure.
Before and after chemical treatment PAH concentrations and PAH bioavailability were
measured. The two approaches led to the following general conclusions on the structure of
amorphous and condensed SOM domains: (1) Condensed SOM is less polar than amorphous
SOM. (2) Labile components like carbohydrates, peptides, fatty acids, and free alkanes are likely
to be associated with the amorphous SOM domain. (3) There is no clear relationship between
aromaticity and the degree of SOM condensation. (4) Condensed SOM is situated in the humin
fraction, indicating that it has a relatively high C content, a relatively low O content, and a
relatively high degree of polymerization. (5) Humic and fulvic acids are primarily associated
with amorphous SOM. (6) Coal and soot are specific condensed facies with a high affinity for
PAHs. Apart from these general characteristics it appeared that the composition of the SOM
domains was highly sample specific.
CONTENTS
CHAPTER 1 1
General Introduction
CHAPTER 2 33
Development of a persulfate oxidation method for the prediction of PAH
bioavailability in soils and sediments
CHAPTER 3 47
Rapid persulfate oxidation predicts PAH bioavailability in soils and sediments
CHAPTER 4 63
Extraction with hydroxypropyl-p-cyclodextrin and Triton X-100 for the
prediction of PAH bioavailability in contaminated sediments
CHAPTER 5 83
Prediction of petroleum hydrocarbon bioavailability in contaminated soils and
sediments
CHAPTER 6 105
Amorphous and condensed soil/sediment organic matter domains. 1. The effect
of persulfate oxidation on the composition of soil/sediment organic matter
CHAPTER 7 125
Amorphous and condensed soil/sediment organic matter domains. 2. The effect
of extraction, hydrolysis, and oxidation on PAH concentrations and PAH
bioavailability
CHAPTER 8 145
General Discussion
SUMMARY 153
SAMENVATTING 157
CHAPTER 1
General Introduction
1.1 Scope of this Thesis 2
1.2 Polycyclic Aromatic Hydrocarbons 3
1.2.1 Structure 3
1.2.2 Sources 3
1.2.3 Physico-Chemical Properties 7
1.2.4 Toxicity 7
1.3 Remediation of PAH Contaminated Soils and Sediments 8
1.3.1 Physical-Chemical Remediation 8
1.3.2 Bioremediation 10
1.3.3 Policy Changes and Perspectives for Bioremediation 11
1.3.4 Factors Affecting PAH Biodegradation 12
1.4 Bioavailability 14
1.4.1 Defining Bioavailability 14
1.4.2 Equilibrium Sorption 15
1.4.3 Desorption Kinetics 20
1.4.4 Measuring Bioavailability 23
1.5 Outline of this Thesis 25
1.6 References 25