Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) and their parent-PAHs in soil [Elektronische Ressource] : analysis, sources and fate / Benjamin Acham Musa Bandowe

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Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) and their parent-PAHs in soil - analysis, sources and fate - Dissertation zur Erlangung des Grades “Doktor der Naturwissenschaften” (im Promotionsfach Chemie) am Fachbereich Chemie, Pharmazie und Geowissenschaften der Johannes Gutenberg-Universität Mainz. Benjamin Acham Musa Bandowe, M. Sc., geboren in Ghana. Leader Dekan: 1. Berichterstatter: 2. Berichterstatter: Tag der mündlichen Prüfung: 29.04.2010 ILeader Contents Contents………………………………………………………………………………………..II List of tables.................................................................................................................... VI List of figures ................................................................................................................VIII List of abbreviations ..........................................................................................................X Acknowlegements .........................................................................................................XIII Summary.......................................................................................................................XIV ZussammenfassungXV A Summarizing overview ...........................................................................................1 1 Introduction ..............................................................................................................2 1.

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Oxygen-containing polycyclic aromatic hydrocarbons
(OPAHs) and their parent-PAHs in soil
- analysis, sources and fate -

Dissertation
zur Erlangung des Grades
“Doktor der Naturwissenschaften”
(im Promotionsfach Chemie)

am Fachbereich Chemie, Pharmazie und Geowissenschaften
der Johannes Gutenberg-Universität Mainz.

Benjamin Acham Musa Bandowe, M. Sc.,

geboren in Ghana.
Leader
Dekan:
1. Berichterstatter:
2. Berichterstatter:

Tag der mündlichen Prüfung: 29.04.2010

ILeader
Contents
Contents………………………………………………………………………………………..II
List of tables.................................................................................................................... VI
List of figures ................................................................................................................VIII
List of abbreviations ..........................................................................................................X
Acknowlegements .........................................................................................................XIII
Summary.......................................................................................................................XIV
ZussammenfassungXV
A Summarizing overview ...........................................................................................1
1 Introduction ..............................................................................................................2
1.1 Polycyclic aromatic hydrocarbons (PAHs) ................................................................2
1.2 Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs)...............................4
1.3 Objectives.................................................................................................................9
2 Materials and methods ............................................................................................11
2.1 Standards and chemicals .........................................................................................11
2.2 Study sites and sampling11
2.3 Physico-chemical characterization of soils ..............................................................12
2.4 Calculations, compound properties and statistical analysis ......................................12
2.5 Analysis of polycyclic aromatic hydrocarbons and their oxygen-containing
derivatives and metabolites in soil (Section B) ........................................................13
2.6 Polycyclic aromatic hydrocarbons (PAHs) and their oxygen-containing derivatives
and metabolites (OPAHs) in soils from the Angren industrial Region, Uzbekistan
(Section C)..............................................................................................................14
2.7 Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) and their parent-
PAHs in Urban soils of Bratislava, Slovakia (Section D).........................................15
3 Results and Discussion............................................................................................16
3.1 Analysis of polycyclic aromatic hydrocarbons and their oxygen-containing
derivatives and metabolites in soils (Section B).......................................................16
3.2 Polycyclic aromatic hydrocarbons (PAHs) and their oxygen-containing derivatives
and metabolites (OPAHs) in soils from the Angren industrial area, Uzbekistan
(Section C)..............................................................................................................17
3.3 Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) and their parent-
PAHs in urban soils of Bratislava, Slovakia (Section D)..........................................19
II Leader
3.4 Concentration, composition pattern, sources and vertical transport of OPAHs in soils
...............................................................................................................................20
3.5 Quality control and error discussion........................................................................22
4 General conclusions ................................................................................................23
5 References ..............................................................................................................25
B Analysis of Polycyclic Aromatic Hydrocarbons and their Oxygen-Containing
Derivatives and Metabolites in Soils.....................................................................34
1 Abstract ..................................................................................................................35
2 Introduction ............................................................................................................36
3 Materials and Methods............................................................................................39
3.1 Soil Samples...........................................................................................................39
3.2 Chemicals and Reagents..........................................................................................39
3.3 Pressurized Liquid Extraction.................................................................................40
3.4 Clean-up/Fractionation and Derivatization..............................................................41
3.5 Gas Chromatography/Mass Spectrometry ...............................................................41
3.6 Quantification of Target Compounds ......................................................................42
3.7 Recovery Experiments and Measurement of Certified Reference Material ..............43
3.8 Method Application................................................................................................43
3.9 Quality Assurance/Control......................................................................................44
4 Results and Discussion............................................................................................44
4.1 Method performance...............................................................................................44
4.1.1 Accuracy and precision of the carbonyl-OPAHs analysis................................44
4.1.2 Accuracy and precision of the hydroxyl/carboxyl-OPAHs analysis.................47
4.1.3 Accuracy and precision of the parent PAHs....................................................49
4.1.4 Limits of detection (LOD)..............................................................................50
4.2 Concentrations of PAHs and OPAHs in selected soil samples .................................52
5 Conclusions ............................................................................................................53
6 Acknowlegments ....................................................................................................54
7 References ..............................................................................................................54
8 Supplemental information (Section B) ....................................................................60
C Polycyclic aromatic hydrocarbons and their oxygen-containing derivatives and
metabolites (OPAHs) in soils from the Angren industrial area, Uzbekistan ......64
1 Abstract ..................................................................................................................65
III Leader
2 Introduction ............................................................................................................66
3 Materials and methods ............................................................................................68
3.1 Description of study location...................................................................................68
3.2 Soil sampling and properties ...................................................................................69
3.3 PAH and OPAH analyses........................................................................................71
3.3.1 Target compounds..........................................................................................71
3.3.2 Analytical method71
3.4 Quality assurance and quality control......................................................................72
3.5 Calculations and compound properties....................................................................73
4 Results....................................................................................................................73
4.1 PAH and OPAH concentrations ..............................................................................73
4.2 Correlations among PAH, OPAH, C , and heavy metal concentrations .................79 org
4.3 Concentration ratios of OPAHs to parent-PAHs……………………………………81
4.4 Depth distribution of PAHs and OPAHs in relation to their hydrophobicity ............83
5 Discussion ..............................................................................................................85
5.1 Spatial distribution of PAH concentrations and relationship with heavy metals .......85
5.2 Spatial variation of the relationship of OPAHs with PAHs and heavy metals ..........88
5.3 Mobility of OPAHs as compared to PAHs ..............................................................90
6 Conclusions ............................................................................................................91
7 Acknowledgments ..................................................................................................92
8 References ..............................................................................................................92
D Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) and their
parent-PAHs in urban soils of Bratislava, Slovakia ............................................98
1 Abstract ...................................................................................................................99
2 Introduction ..........................................................................................................100
3 Materials and methods ..........................................................................................101
3.1 Soil sampling and soil properties...........................................................................101
3.2 OPAH and PAH analysis ......................................................................................105
3.3 Quality assurance and quality control....................................................................106
3.4 Calculations and compound properties..................................................................106
4 Results..................................................................................................................107
4.1 Concentrations of OPAHs and PAHs in topsoils ...................................................107
4.2 Depth distribution of OPAHs and PAHs ...............................................................112
IV Leader
5 Discussion ............................................................................................................113
5.1 State of contamination of the urban soils of Bratislava with OPAHs and PAHs.....113
5.2 Sources of OPAHs and PAHs ...............................................................................115
5.3 Importance of OPAHs relative to parent-PAHs ....................................................116
5.4 Vertical distribution of OPAHs and PAHs............................................................116
6 Conclusion116
7 Acknowledgement ................................................................................................117
8 References ............................................................................................................117
E Appendix.............................................................................................................123
E-1 Naphthalene production by microorganisms associated with termites: evidence from
a microcosm experiment .......................................................................................124
E-2 Method optimization to measure polybrominated diphenyl ether (PBDE) in soils of
Bratislava, Slovakia ..............................................................................................155
E-3 Appendix tables .....................................................................................................186
Curriculum vitae ..............................................................................................................196

VLeader
List of tables
-1Table A-1: Concentrations [ng g ] of OPAHs and alkyl/parent-PAHs in soils……………21
Table B-1: Concentrations (mean±standard deviation) of OPAHs in Manaus, Mainz and
®Berlin (ERM -CC013a) soils, precision (RSD, n = 8), and limits of detection
(LODs) of the used method. Only compounds with accepted recoveries are
reported (see text)………………………………………………………………47
Table B-2: Concentrations (mean±standard deviation) of PAHs in Manaus, Mainz and
®Berlin (ERM -CC013a) soils with certified values, precision (RSD, n = 3) and
limits of detection (LODs) of the used method. Reference values in parentheses
are non-certified indicative values without uncertainty statement…………….51
Table B-3: Type (IUSS Working Group WRB, 2006) and selected properties of soil used in
method development, validation and application. Soil texture, total organic
®carbon (C ), and pH of ERM -CC013a were determined by BAM (Berlin, org
Germany) available in certification reports online (http://www.rm-
certificates.bam.de/en/certificates/environment/index.htm)...............................60
Table B-4: List of OPAHs and fluoranthene-D , purity, supplier, and SIM ions used for 10
their quantification. Compounds are arranged in ascending order of retention
times for carbonyl and hydroxyl/carboxyl-OPAHs and numbered accordingly
(in brackets). Deuterated internal standards are shown in italics………………61
Table B-5: List of target PAHs their deuterium-labelled PAHs, purity, supplier and ions
used for their measurements. Target PAHs are arranged in ascending order of
retention times and numbered accordingly (in parentheses). Each group of PAHs
is quantified relative to the labeled deuterated PAH before it…………………62
Table C-1: Sampling locations, land use and selected physico-chemical properties of soil.
Sampling depth 1 is at 0-10 cm and 2 at 10-20 cm depth……………………...70
Table C-2: Concentration of individual OPAHs and KEPA-PAH and K21PAHs at the 11
study sites (ng/g). Sampling depth 1 is at 0-10 cm and 2 at 10-20 cm depth…..78
Table C-3: Pearson correlation coefficient for K31PAHs, K7 carbonyl-OPAHs, K5
hydroxyl-OPAHs and selected trace metals in top soils (n = 8)……………….81
Table C-4: Ratios of concentration of OPAH metabolite to parent-PAH (from which the
metabolite is derived during metabolism) at different sites……………………82
Table C-5: PAHs concentrations (ng/g) in soils from other industrial areas in the world
(ranges or means ± standard deviations)……………………………………….87
VI Leader
Table D-1: Sampling locations, horizons and land use of Bratislava soils………………..103
-1Table D-2: Physico-chemical soil properties and total concentrations (ng g ) of PAHs,
carbonyl-OPAHs and hydroxyl-OPAHs in Bratislava soils…………………..104
Table D-3: Concentration ratios of OPAHs to their parent-PAHs in soils of Bratislava.
Labels ending with “t” refer to surface soil horizon and “s” refers to subsoil
horizon. Subsoil horizon is given as mean and range (brackets) of all subsoil
horizons at particular sampling sites….………………………………………111
Table D-4: Comparison of OPAH and PAH concentrations in surface soil horizons of
Bratislava with other cities……………………………………………………114

VII Leader
List of figures
Figure A-1: Description of the main processes affecting the fate of POPs in the soil
ecosystem (modified from Moeckel et al., 2008)………………………………..3
Figure A-2: Photoxidation of benzo[a]pyrene leading to formation of OPAHs (Nikolaou et
al., 1984)…………………………………………………………………………4
.Figure A-3: Reaction of ANTH with O (a) and NAPH with OH (b) to form OPAHs 3
(Perraudin et al., 2007; Lee and Lane, 2009)……………………………………5
Figure A-4: Microbial degradation pathways of PAHs under aerobic conditions (Cerniglia,
1992)……………………………………………………………………………..6
Figure A-5: Schematic representation of the mechanism of toxicity of OPAHs (Bolton et
al., 2000)7
Figure A-6: Schematic description of the optimized analysis procedure for alkyl/parent-
PAHs and OPAHs in soil………………………….…………………………...14
Figure A-7: Relation between KOPAHs and Kalkyl/parent-PAHs in Angren surface soils
(closed box) and Bratislava surface soils (open boxes)………………………..21
Figure B-1: Recoveries of carbonyl-OPAHs [A] and hydroxyl/carboxyl-OPAHs [B] from
spiked soils. Error bars indicate the standard deviation of replicates (n=8)……46
-1Figure B-2: The GC/MS-SIM chromatogram of the standard mixtures (500 ng ml ) of
carbonyl-OPAHs [A], hydroxyl/carboxyl-OPAHs [B], and alkyl/parent-PAHs
[C]. Fluoranthene-D is included in all three chromatograms at different 10
positions. Numbering for alkyl/parent-PAH and carbonyl and
hydroxyl/carboxyl-OPAHs is the same as shown in Tables B-4 and B-5,
respectively……………………………………………………………………..63
Figure C-1: Location of the study area (aerial photo is from Google Earth) with sampling
sites A-K described in Table C-1………………………………………………68
Figure C-2: Concentrations of K31PAHs (A), K7 carbonyl-OPAHs (B), and K5 hydroxyl-
PAHs in topsoil (0-10 cm, filled black bars) and subsoil (10-20 cm, open bars)
of the 11 study sites…………………………………………………………….74
Figure C-3: Composition [%] of parent- and alkylated PAH mixtures in topsoil (0-10 cm,
filled black bars) and subsoil (10-20 cm, open bars) of the 11 sampling sites A-
K depicted in Figure C-1………………………………………………………75
VIII Leader
Figure C-4: Percentage contribution of 2-+3-, 4-, 5-, and 6-+7-ring parent-PAHs to the sum
of 21 parent-PAHs (K21PAHs) in topsoils (upper diagram) and subsoils (lower
diagram)………………………………………………………………………...77
Figure C-5: Relation between K7carbonyl-OPAHs (closed boxes), K5hydroxyl-OPAHs
(open boxes), and K31PAHs (upper diagram), and relation between Khydroxyl-
OPAHs and Kcarbonyl-OPAHs (lower diagram)……………………………...80
Figure C-6: Box plots of mean concentration ratios [CR] of PAHs and OPAHs of the 11
sampling points. CR is concentration ratio of individual PAH or OPAH in the
subsoil to that of same compound in topsoil. Boxes define the range, the central
line represents the median. Outliers (open circles) and extreme values (stars) are
also shown……………………………………………………………………...84
Figure D-1: Location of sampling sites in Bratislava……………………………………….102
Figure D-2: Composition of the carbonyl-OPAHs mixtures in soils of Bratislava…………109
Figure D-3: Composition of the alkyl/parent-PAH mixtures in soils of Bratislava…………110

IX