Non-target screening of extractable and non-extractable organic xenobiotics in riverine sediments of Ems and Mulde Rivers, Germany

Article abstract of DOI:10.1016/j.envpol.2006.08.014

Subaquatic sediment samples derived form Elbe and Mulde Rivers, Germany, were analyzed for extractable and non-extractable anthropogenic organic compounds by a non-target screening approach. Applied methodologies were gas chromatography-mass spectrometry, dispersion extraction and degradation procedures, particularly alkaline and acidic hydrolysis, boron tribromide treatment, ruthenium tetroxide oxidation as well as pyrolysis and TMAH (tetramethylammonium hydroxide)-thermochemolysis. Numerous compounds were identified, including halogenated benzenes, anisoles, styrenes, alkanes, diphenylmethane derivates, anilines, phenols and diphenyl ethers. The results were interpreted with respect to compound specific modes of incorporation as well as to potential sources (e.g. municipal, agricultural, industrial). Extractable and non-extractable fractions differed significantly with respect to their qualitative and quantitative composition. For example, quantities in the extractable and non-extractable fractions of chlorinated benzenes differed up to factor 50. Among other significant results, the investigation revealed hints for a dependence of the mode of incorporation of chlorinated benzenes on their substitution pattern.

Full text of DOI:10.1016/j.envpol.2006.08.014

Environmental Pollution 147 (2007) 176e186
www.elsevier.com/locate/envpol
Non-target screening of extractable and non-extractable organic
xenobiotics in riverine sediments of Ems and Mulde Rivers, Germany
*
Alexander Kronimus , Jan Schwarzbauer
Institute of Geology and Geochemistry of Petroleum and Coal, RWTH Aachen University, Lochnerstr. 4-20, D-52056 Aachen, Germany
Received 16 March 2006; received in revised form 19 July 2006; accepted 2 August 2006
Analysis of both, extractable and non-extractable fraction of organic xenobiotics in sediments reveals a more
detailed and comprehensive anthropogenic load profile.
Abstract
Subaquatic sediment samples derived form Elbe and Mulde Rivers, Germany, were analyzed for extractable and non-extractable anthropo-
genic organic compounds by a non-target screening approach. Applied methodologies were gas chromatographyemass spectrometry, dispersion
extraction and degradation procedures, particularly alkaline and acidic hydrolysis, boron tribromide treatment, ruthenium tetroxide oxidation as
well as pyrolysis and TMAH (tetramethylammonium hydroxide)-thermochemolysis. Numerous compounds were identified, including haloge-
nated benzenes, anisoles, styrenes, alkanes, diphenylmethane derivates, anilines, phenols and diphenyl ethers. The results were interpreted with
respect to compound specific modes of incorporation as well as to potential sources (e.g. municipal, agricultural, industrial). Extractable and
non-extractable fractions differed significantly with respect to their qualitative and quantitative composition. For example, quantities in the
extractable and non-extractable fractions of chlorinated benzenes differed up to factor 50. Among other significant results, the investigation
revealed hints for a dependence of the mode of incorporation of chlorinated benzenes on their substitution pattern.
Ó 2006 Elsevier Ltd. All rights reserved.
Keywords: Organic pollutants; Bound residues; Riverine sediments; GCeMS; Degradation
1. Introduction
bound residues are associated with carrier molecules by differ-
ent types of interactions. The most important ones are revers-
ible adsorptive and van-der-Waals forces, charge transfer
complexes of aromatic p-systems as well as reversible or irre-
versible covalent bonds (e.g. Michaelis et al., 1995; Richnow
et al., 1994, 1997; Roberts, 1984). By investigating stable car-
bon isotope ratios of n-alkanes in soils, different ages and turn-
overs of the compounds in the extractable and non-extractable
fraction have been revealed (Lichtfouse et al., 1998; Licht-
fouse, 1999). Bound residues are principally immobile and
of a limited or absent biovailability (Northcott and Jones,
2000). The major quantity of bound residues in sediments
are thought to be incorporated reversibly, implying the classi-
fication of the phenomenon as a temporary sink for contami-
nants on the one hand. On the other hand, bound residues
recover an additional contamination potential, which is not
Non-target screening approaches facilitate comprehensive
gathering of anthropogenic contaminants including so far un-
noticed or unknown structures. Several corresponding investi-
gations of riverine systems and estuaries have been reported
(Bester et al., 1997; Kronimus et al., 2004; Schwarzbauer
et al., 2000). However, these investigations regarded the ex-
tractable fraction, exclusively. In sediments as well as in soils,
low molecular weight organic compounds can be affected by
intermolecular interactions with geomacromolecules (e.g. hu-
mic compounds), preventing their extraction. These so-termed
* Corresponding author. Tel.: þ49 241 809 8295; fax: þ49 241 809 2152.
E-mail addresses: kronimus@lek.rwth-aachen.de (A. Kronimus), schwar
zbauer@lek.rwth-aachen.de (J. Schwarzbauer).
0269-7491/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2006.08.014

A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
177
concerned by conventional analyzes, considering extractable
compounds, only.
Sealed vessel pyrolysis and TMAH-thermochemolysis have
been widely applied in organic geochemistry for characterizing
structural properties of geomacromolecules (e.g. Garcette-
Lepecq et al., 2001; Kralert et al., 1995; Pulchan et al., 2003).
The present investigation was focused on the comprehen-
sive characterization of the anthropogenic contamination
within the analyzed sediments by analysis of extractable and
non-extractable anthropogenic organic compounds. A second
aim was to determine potential emission sources of the identi-
fied compounds. Chemical degradation approaches concerning
riverine sediments have been previously applied on samples
from the Teltow Canal, Berlin (Schwarzbauer et al.,
2003a,b), but are generally rare.
Methodologically, two principal approaches are suitable for
analyzing bound residues. First, non-destructive spectroscopic
methods, e.g. NMR and FTIR spectroscopy, facilitate character-
ization of interactions between bound residues and associated
macromolecules. Spectroscopic approaches are particularly ap-
propriate for laboratory experiments on isotope-labeled com-
pounds. However, application on natural samples is limited by
interferences of specific signals with background noise of nu-
merous naturally occurring constituents. Second, destructive
methods are applicable, which on the one hand are targeting
on release of bound residues by cleaving interactions between
incorporated compounds and macromolecular carrier mole-
cules. On the other hand, destructive methods can be effective
by degrading present macromolecular structures while incorpo-
rated low molecular compounds are remaining stable during the
treatment. However, interactions between bound residues and
geomacromolecules will be degraded in any case. Conse-
quently, the chemical nature of incorporations can only be de-
termined indirectly, by interpretation of the molecular
structures of generated degradation products. This is a signifi-
cant difference to non-destructive methods. One advantage of
destructive methods is the possibility of a subsequent applica-
tion of established trace analysis, e.g. gas chromatographye
mass spectrometry with preliminarily executed fractionation
or clean up procedures. More details of analytical methods for
analysis of bound residues are described by Northcott and Jones
(2000) and references cited therein.
2. Materials and methods
2.1. Sampling
Three subaquatic surface sediment samples with a maximum depth of 15 cm
were taken from Mulde River, East-Germany, and one from Ems River,
Northwest-Germany (Fig. 1). For quantification, dry weights of the sediments
were determined. Both rivers are effected by industrial effluents (Schwarzbauer
et al., 1999).
2.2. Chemicals and reagents
All chemicals, reagents and solvents were purchased from Sigma Aldrich
(Taufkirchen, Germany), Merck (Darmstadt, Germany) and ABCR (Karlsruhe,
Germany). Methylclorofen (2-benzyl-4-chloroanisol) was synthesized by
reaction of 2-benzyl-4-chlorophenol with dimethyl sulphate under alkaline
Within the present investigation, the extractable fractions of
four subaquatic sediment samples derived from Ems and
Mulde Rivers, Germany, were investigated. Additionally, the
extracted sample residues were sequentially treated by alka-
line and acidic hydrolysis, BBr3-degradation and finally
RuO4-Oxidation. Furthermore, sealed-vessel pyrolysis and
thermochemolysis with assistance of tetramethyl ammonium
hydroxide (TMAH) were applied on aliquots of preextracted
sediments. Analytical investigations of the extractable as
well as the non-extractable fractions were performed as non-
target screening approaches, based on GCeMS. From the
abundant spectrum of detected compounds, selected ones
were quantified. Treatment by hydrolysis affords release of
compounds incorporated by ester bonds. Remaining com-
pounds, still incorporated by ester and ether bonds can be re-
leased by subsequent BBr3-treatment. The present types of
interactions can be distinguished by the structural properties
of occurring products after degradation treatment. Compounds
incorporated by ether bonds result in generation of alcohols
and halogenides, whereas the products of ester cleavages are
alcohols and carbon acids (Bhatt and Kulkarni, 1983; Richnow
et al., 1994). RuO4-oxidation facilitates degradation of aromatic
structures and activated carbon-carbon bonds (Richnow et al.,
1992; Stock and Tse, 1983). Additionally, the described degra-
dation techniques can contribute to the release of bound residues
by degrading specific structural configurations within carrier
macromolecules, e.g. ether and ester bonds or aromatic struc-
tures, leading to the destruction of the affected macromolecules.
Fig. 1. Map of Germany with Ems and Mulde Rivers as well as the sampling
sites.

178
A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
conditions. Solvents were distilled and purity was checked by gas chromatog-
raphy before using.
and concentrated before fractionation on silica gel columns with dichlorome-
thane and methanol. To each fraction, 50 ml of an internal standard solution,
containing 5 ng/ml d34-hexadecane was added. The methanol fraction was
treated with a methanolic diazomethane solution for methylation of acidic
groups.
2.3. Extraction, fractionation and recoveries
Aliquots of approximately 10 g of untreated wet sediment were extracted
five times by a sequential dispersion extraction with solvent mixtures of acetone
and hexane. The combined extracts were volume reduced by rotary evaporation,
dried with granular anhydrous Na2SO4 and desulphurized by addition of acti-
vated copper powder. Subsequently, the extracts were fractionated on silica
gel microcolumns by elution with six different mixtures of n-pentane, dichloro-
methane and methanol. To each fraction, 50 ml of an internal standard mixture,
containing d34-hexadecane, d10-pyrene and d12-chrysen (each 5.0 ng/ml) in
n-hexane were added. The methanol fraction was treated with a methanolic
diazomethane solution in order to methylate acidic groups. Recoveries were
determined by four spiking experiments on annealed sediments. More details
of the applied procedures are described elsewhere (Schwarzbauer et al., 2000).
2.4.2. Acidic hydrolysis
20 ml of 4N hydrochloric acid was added to 2 g sample residue derived
from alkaline hydrolysis treatment in a glass vessel, which was subsequently
closed hermetically and heated for 24 h at 105 ꢀC. After cooling and sonica-
tion the liquid phase was decanted into a separatory funnel and 50 ml of
HPLC grade water was added. The solid residue was extracted sequentially
with methanol, dichloromethane and n-pentane by sonication and the extracts
were combined with the preliminarily decanted acidic phase. Thereafter, the
combined solutions were extracted three times with dichloromethane. The lat-
ter phase was dried, concentrated and fractionated on silica gel columns by the
following eluants: 1. n-pentane:dichloromethane (1:1 v/v); 2. dichlorome-
thane; and 3. methanol. To each fraction, 50 ml of an internal standard solution,
containing 5 ng/ml d34-hexadecane was added.
2.4. Degradation procedures
2.4.3. Boron tribromide treatment
Chemical degradation procedures were performed sequentially with re-
spect to each sediment sample after treatment by dispersion extraction as de-
scribed above. Pyrolysis and TMAH-thermochemolysis were performed on
preextracted and non-degraded samples only. The workflow is illustrated in
Fig. 2.
Boron tribromide solution in dichloromethane was added to approximately
2 g of sediment which was preliminarily extracted and treated by alkaline and
acidic hydrolysis. The suspension was sonicated for 2 h, then stirred at room
temperature for 24 h and finally sonicated again. After addition of 5 ml of di-
ethyl ether, the mixture was decanted and filtrated. The solid residue was
washed twice with diethyl ether and the combined wash solutions were added
to the filtered reaction mixture. The mixture was washed and dried and subse-
quently concentrated by rotary evaporation. Thereafter, the solution was frac-
tionated on silica gel columns by elution of the following solutions:
1.n-pentane:dichloromethane (95:5 v/v); 2. dichloromethane; and 3. meth-
anol. To each fraction, 50 ml of an internal standard solution, containing 5
ng/ml d34-hexadecane were added.
2.4.1. Alkaline hydrolysis
Approximately 2 g of preextracted sediment was added to a mixture of
methanol (7 ml), HPLC grade water (200 ml) and 250 mg potassium hydroxide
in a glass vessel, which was subsequently closed hermetically. The mixture
was heated for 24 h at 105 ꢀC. After cooling and filtration, the solution was
acidified with hydrochloric acid to pH-values between 3 and 5, and extracted
three times with dichloromethane. The combined organic layers were dried
2.4.4. Ruthenium tetroxide oxidation
To sample residues from BBr3-treatment, 500 mg NaIO4, 10 mg RuO4,
8 ml of carbon tetrachloride, 8 ml of acetonitrile as well as 1 ml HPLC grade
water were added. The mixture was stirred for 4 h at room temperature. There-
after, the reaction was stopped by addition of 50 ml methanol and the same vol-
ume of concentrated sulfuric acid. The mixture was decanted, filtered and the
residue was washed three times with carbon tetrachloride. Subsequently, the
mixture was stirred for 24 h at room temperature. After addition of 5 ml
HPLC grade water, the CCl4-phase was separated, the remaining aqueous ace-
tonitrile phase was washed three times with diethyl ether and the washing so-
lution was combined with the CCl4-phase. The combined organic layers were
concentrated by rotary evaporation and iodine was removed by addition of so-
dium thiosulfate. The aqueous layer was carefully removed by pipettation. The
remaining solution was dried and concentrated to 0.5 ml. The subsequent frac-
tionation on silica gel columns was carried out by elution with dichlorome-
thane and an a mixture of diethyl ether and methanol (2:3 v/v). To each
fraction, 50 ml of an internal standard solution, containing 5 ng/ml d34-hexade-
cane were added.
2.4.5. Pyrolysis and TMAH-thermochemolysis
Approximately 150 mg of each pre-extracted sample was transferred into
a glass tube. Additionally, 200 ml of a 20% methanolic tetramethylammonium
hydroxide (TMAH) solution was added and the mixture was suspended by
shaking the tubes gently. Pyrolyses procedures were analogous to those of
TMAH-thermochemolyses, but without introduction of TMAH into the glass
tubes. Methanol and oxygen were removed by a gentle stream of nitrogen. Af-
ter sealing the tubes, those were heated for 30 min at 250 ꢀC and, thereafter,
cooled to ꢁ18 ꢀC. The tubes were opened and 1 ml of n-hexane was added
to the thermodegraded sample residue. This mixture was sonicated for
3 min. After washing the inner vessel surface with n-hexane, the extract was
decanted into a glass flask. The sample and the vessel surface were washed
again with 1 ml n-hexane and the organic solutions were combined. The ex-
traction procedure was repeated with acetone. To the combined solutions,
Fig. 2. Workflow of the applied analytical procedure.

A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
179
approx. 5 ml of n-hexane were added and acetone was removed by rotary
evaporation, followed by drying the resulting n-hexane phase by elution on
a microcolumn, packed with anhydrous NaSO4.
sediments analyzed, with unequal concentrations. Maximum
concentration was 700 mg/kg for hexachlorobenzene in sample
E1. With respect to the non-extractable fraction, the results
after boron tribromide treatment of samples M1 and M3 are
distinctive, due to the fact that di- and trichlorinated benzenes
are characterized by quantities of up to almost 50 times higher
than within the extractable phase. On the other hand, sample
E1, affected by the highest extractable contamination with
di- and trichlorobenzenes, is characterized by contrary propor-
tions (Tables 2 and 3). The analytical results after boron tribro-
mide treatment indicate the incorporation of lower chlorinated
benzenes, particularly dichlorobenzene, by ether bonds with
variable proportions of extractable and non-extractable spe-
cies. This hypothesis is supported by the occurrence of bromo-
dichlorobenzene in samples M1, M3 and E1 after boron
tribromide degradation, because this mixed halogenated ben-
zene can be derived from an incorporation of dichlorobenzene
by an ether functionality (see Fig. 4). Dichlorobenzenes are
frequently detected contaminants in riverine and estuarine sed-
iments (Heim et al., 2004; Ianuzzi et al., 2004; Kronimus
et al., 2004; Lee and Fang, 1997; Schwarzbauer et al., 2000,
2001). Therefore, the partially dominating non-extractable
portions of dichlorobenzenes observed in our study are indi-
cating that those might act as reservoirs, able to compensate
biotically or abiotically reduced pools of extractable dichloro-
benzenes. Benzenes with four to six chlorine substituents were
also present in the bound state revealed by pyrolysis. There is
no hint for tetra- and pentachlorobenzenes incorporated by
ether bonds. Consequently, other modes of incorporation
have to be assumed, for example charge transfer complexa-
tion. This is also valid for hexachlorobenzene, providing no
protons for electrophilic substitutions, which is a condition
for a covalent incorporation. A thermodynamical reason for
a preferentially non-etherical incorporation of higher chlori-
nated benzenes might be a deactivation of the aromatic system
due to an incremental Iꢁ-effect, caused by an increasing num-
ber of chlorine substituents, preventing naturally occurring
electrophilic attacks on the p-system.
The extracts were fractionated into four fractions on silica gel microcol-
umns, using mixtures of pentane, dichloromethane and methanol. Subse-
quently, 50 mL of an internal standard mixture, containing d34-hexadecane
(5.0 ng/ml) in n-hexane were added to each fraction.
2.5. Gas chromatographyemass spectrometry (GCeMS)
GCeMS analyzes were performed on a Trace MS (ThermoElectron,
Egelsbach, Germany) single quadrupol mass spectrometer linked to
a HRGC5160 gas chromatograph (Carlo Erba, Milano, Italy), equipped with
a Zebron ZB-5 ms (Phenomenex, Aschaffenburg, Germany) capillary column
(30 m ꢂ 0.25 mm ꢂ 0.25 mm) and was programmed as follows: 3 min isother-
mal time at 60 ꢀC, followed by heating with 3 K/min to 310 ꢀC. Temperature of
the split/splitless injector was 270 ꢀC, splitless time was 60 s and helium carrier
gas flow was 1.5 ml/min. The mass spectrometer operated with electron impact
ionization (EIþ, 70 eV) and in full scan mode, scanning from 35 to 700 amu
with a scan time of 0.67 s. Interface temperature was 270 ꢀC and source tem-
perature was 200 ꢀC. Regarding fractions derived from extracts and chemical
degradation procedures, approximately 1 ml were injected out of a solution vol-
ume of 50 ml. Limit of quantification (signal:noise ¼ 10:1) was 0.5 mg/kg,
whereas the limit of detection was 0.2 mg/kg. Fractions derived from TMAH-
thermochemolysis and pyrolysis were injected completely. There, limit of
quantification (signal:noise ¼ 10:1) was 0.1 mg/kg, whereas limit of detection
was 0.03 mg/kg. Compound identification was performed by comparison of
mass spectra with digital libraries (NIST/EPA/NIH, Mass Spectral Library
NIST2002, Wiley/NBS Registry of Mass Spectral Data, 7th Ed., electronic ver-
sions) or by comparing gas chromatographic and mass spectrometric properties
of analytes with those of reference compounds. Quantification was performed
by comparing integrals of two representative ions (see Table 1) of each analyte
with those of externally calibrated (4 points) reference compounds.
3. Results and discussion
Within the investigation, a wide spectrum of organic con-
taminants have been gathered, which are listed in Table 1.
The corresponding molecular structures are given in Fig. 3.
The qualitative and quantitative results are given in Tables 2
and 3. In the following, the analytical results are presented
and interpreted according to the compounds’ affinity for incor-
poration into macromolecular matrices and corresponding
types of chemical interactions as well as potential emission
sources.
Anthropogenic compounds were not detected following
acidic and alkaline degradations under the analytical condi-
tions used. This fact implies two conclusions. First, there are
no hints for bound residues incorporated by hydrolyzable in-
teractions. Second, a release of incorporated compounds by
degradation of hydrolyzable moieties of potential carrier mac-
romolecules has not been observed. Consequently, variation of
pH of the pore water of the sediments at the sampling sites in-
vestigated would not result in a significant transfer of bound
residues into the extractable fraction. Also decontamination
by alkaline/acidic treatment would be marginally effective.
For occurrence of dibromobenzene, bromoxylene and bro-
moethylbenzene, which were exclusively detected after boron
tribromide degradation, two origins are conceivable. On the
one hand, the brominated compounds could have been incor-
porated non-covalently. On the other hand, the compounds
could have been incorporated by ether bonds as non-bromi-
nated aromatics and been bromitated during boron tribromide
treatment analogous to the reaction mechanism given in Fig. 4.
Additionally, dibromobenzene could have been incorporated
by an ether functionality as monobromobenzene and been di-
brominated by the same reaction. Principally, halogenated
benzenes can be derived from multiple sources do to their
use for different technical purposes.
3.2. Halogenated anisoles
3.1. Halogenated benzenes
Chlorinated anisoles with one to three chlorine substituents,
as well as bromo- and dibromoanisoles have been detected after
TMAH-thermochemolysis, exclusively (see Tables 2 and 3).
Chlorinated benzenes with two to six chlorine substituents
occurred ubiquitously within the extractable fraction of all

180
A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
Table 1
List of compounds, recoveries and ions used for quantification
Compound
Ions (m/z) Structure # Recovery (%) Remarks
Halogenated benzenes Dichlorobenzene
Trichlorobenzene
146, 148
180, 182
214, 216
250, 252
284, 286
224, 226
234, 236
184, 186
184, 186
1
1
1
1
1
2
3
4
5
19
32
42
59
81
3 isomers detected
3 isomers detected
2 isomers detected
Tetrachlorobenzene
Pentachlorobenzene
Hexachlorobenzene
Bromodichlorobenzene
Dibromobenzene
Bromoxylene
Bromoethylbenzene
calibration data kept from bromoxylene
Halogenated anisoles Chloroanisole
Dichloroanisole
Trichloroanisole
142, 144
176, 178
195, 197
186, 188
251, 266
6
6
6
7
7
3 isomers detected
5 isomers detected
3 isomers detected
3 isomers detected
Bromoanisole
Dibromoanisole
Chlorinated styrenes Dichlorostyrene
Trichlorostyrene
Pentachlorostyrene
172, 174
206, 208
276, 278
310, 312
344, 346
378, 380
8
8
8
8
8
8
30
3 isomers detected
calibration data and recovery kept from dichlorostyrene
calibration data and recovery kept from octachlorostyrene
calibration data and recovery kept from octachlorostyrene
calibration data and recovery kept from octachlorostyrene
Hexachlorostyrene
Heptachlorostyrene
Octachlorostyrene
88
32
Halogenated alkanes 1,1,2,2-Tetrachlorethane
Hexachloroethane
83, 85
9
201, 203 10
225, 227 11
177, 179 12
171, 173 13
recovery kept from hexachloro-1,3-butadiene
Hexachloro-1,3-butadiene
Pentachlorocyclopropane
Bromoform
1,2-Dibromo-1,1,2-trichloroethane 211, 213 14
DDT-metabolites
Anilins/phenols
DDE
DDNS
DBP
316, 318 15
235, 237 16
139, 141 17
190, 192 18
248, 250 19
236, 238 20
89
2 isomers detected
calibration data and recovery kept from 4,4-DDD, 2 isomers
77
90
DDCN
DDNU
DDM
2 isomers detected
2 isomers detected
3 isomers detected
54
Dichloroanilin
161, 163 21
329, 331 22
Tribromoanilin
4-Chloroionol
4-Bromoionol
225
23
calibration data kept from bromoionol
269, 271 24
330, 332 25
2,4,6-Tribromophenol
Diphenyl ethers
Miscellaneous
Phenoxybenzene
Methylclorofen
141, 170 26
197, 232 27
63
Chlorophenoxyanisole
Dichlorophenoxyanisole
234
268
28
28
calibration data kept from methylclorofen
calibration data kept from methylclorofen
Chloropropiophenone
Dibromoacetonitrile
3,30-Diisopropylbiphenyl
Dimethylsulfone
111, 139 29
118, 120 30
223, 238 31
30
56
2 isomers detected
79, 94
32
N-Formylpiperidine
Tetrabutyl tin
112, 113 33
177, 179 34
220, 222 35
39
Tetrachlorthiophen
Tetramethyl urea
72, 116
36
Corresponding molecular structures are shown in Fig. 3.
The compounds appeared in all samples with concentration
levels of up to 16 mg/kg. Their generation is conceivable
by two pathways. On the one hand e similar to the conclu-
sion on brominated benzenes e on origin of release of non-
covalent incorporated halogenated phenols is possible, which
were methylated to corresponding anisoles by TMAH. On
the other hand, those can be derived from halogenated
benzenes incorporated by ether functionalities. The ether inter-
action could have been cleaved during thermochemolysis and
generated phenolate ions derivated to corresponding anisoles.
The latter hypothesis is much more likely, because etherically
incorporated di- and trichlorobenzenes are proven by the ap-
plied boron tribromide degradations. The existence of incorpo-
rated bromophenol by ether bonds, which is indicated by

A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
181
Fig. 3. Molecular structures of the detected compounds.
occurrence of bromoanisole in post-thermochemolysis extracts,
is in accordance with the occurrence of dibromobenzene after
boron tribromide treatment by reaction pathways described
above. Furthermore, the enzyme catalyzed incorporation of
phenols into humic material by oxidative coupling is a known
process (Park et al., 1999).
detected, released after pyrolysis. Consequently, the results in-
dicate only a limited affinity of chlorinated styrenes for incor-
poration. The analytical data revealed no detailed information
on modes of present interactions with geomacromolecules in
the bound state.
Octachlorostyrene (OCS) as well as penta-, hexa- and hep-
tachlorostyrenes have been identified as by-products from
electrolytical processes with chlorine salts and graphite anodes
(Kaminsky and Hites, 1984; Lunde and Ofstad, 1976) and are
therefore source specific for effluents discharged by chloro-
chemical production plants. These contaminants, particularly
OCS, have been multiply detected in sediments and organisms
(Bester et al., 1998; Kaminsky and Hites, 1984; Kronimus
et al., 2004; Lunde and Ofstad, 1976). More details on chlori-
nated styrenes are described elsewhere (Bester et al., 1998).
3.3. Chlorinated styrenes
Chlorinated styrenes were detected in extracts of samples
E1, M1 and M3 (Tables 2 and 3). While sediments of the
Mulde River are affected by di- and trichlororinated isomers,
derivates with five and more chlorine substituents occurred
in the sample of the Ems River. Penta- and hexachlorostyrenes
(up to 0.2 mg/kg) were the only non-extractable portions

182
A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
Table 2
Quantitative data of samples M1 and M2
Compound
M1
E
M2
E
BBr3
RuO4
Pyr
TCH
BBr3
RuO4
Pyr
TCH
Halogenated benzenes
Dichlorobenzene
Trichlorobenzene
Tetrachlorobenzene
Pentachlorobenzene
Hexachlorobenzene
Bromodichlorobenzene
Dibromobenzene
Bromoxylene
9
5
420
240
13
2
<0.5
3
<0.5
13
4
4
0.6
2
1
<0.5
1
0.1
0.1
<0.5
<0.5
0.1
0.1
26
11
38
94
<0.5
1
Bromoethylbenzene
<0.5
Halogenated anisoles
Chlorinated styrenes
Chloroanisole
Dichloroanisole
Trichloroanisole
Bromoanisole
Dibromoanisole
3
16
2
3
1
<0.1
0.4
0.4
Dichlorostyrene
6
8
Trichlorostyrene
Pentachlorostyrene
Hexachlorostyrene
Heptachlorostyrene
Octachlorostyrene
Halogenated alkanes
DDT-metabolites
Anilins/phenols
1,1,2,2-Tetrachlorethane
Hexachloroethane
120
2
44
<0.5
15
8
Hexachloro-1,3-butadiene
Pentachlorocyclopropane
Bromoform
2
770
36
6
170
4
<0.5
14
1,2-Dibromo-1,1,2-trichloroethane
DDE
DDNS
DBP
2
<0.5
4
0.1
<0.5
DDCN
DDNU
DDM
13
<0.5
<0.5
<0.5
0.6
0.1
Dichloroanilin
Tribromoanilin
4-Chloroionol
<0.5
<0.5
<0.1
<0.1
3
36
5
4-Bromoionol
2,4,6-Tribromophenol
21
Diphenyl ethers
Miscellaneous
Phenoxybenzene
Methylclorofen
5
3
1
3
0.4
0.2
0.1
0.3
0.1
0.1
Chlorophenoxyanisole
Dichlorophenoxyanisole
Chloropropiophenone
Dibromoacetonitrile
3,30-Diisopropylbiphenyl
Dimethylsulfone
2
6
<0.5
<0.5
290
93
N-Formylpiperidine
Tetrabutyl tin
2
0.3
280
2
Tetrachlorothiophen
Tetramethyl urea
<0.1
0.1
25
840
E ¼ Extractable fraction; BBr3 ¼ after boron tribromide treatment; RuO4 ¼ after ruthenium teroxide oxidation; Pyr ¼ after pyrolysis; TCH ¼ after thermochemol-
ysis. All data are given in mg/kg.
3.4. Halogenated alkanes
thermochemolysis. The highest concentration of 120 mg/kg was
determined in sample M1 after pyrolysis. Hexachloroethanewas
detected exclusively within the extractable fraction in samples
E1 and M3, with concentrations of up to 36 mg/kg (Tables 2
and 3). In contrast, in samples M1 and M2, the compound
Halogenated alkanes were predominantly detected in the
non-extractable fraction. In particular, 1,1,2,2-tetrachloroethane
was detected after ruthenium tetroxide oxidation, pyrolysis and

A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
183
Table 3
Quantitative data of samples M3 and E1
Compound
M3
E
E1
E
BBr3
RuO4
Pyr
TCH
BBr3
RuO4
Pyr
TCH
Halogenated benzenes
Dichlorobenzene
Trichlorobenzene
Tetrachlorobenzene
Pentachlorobenzene
Hexachlorobenzene
Bromodichlorobenzene
Dibromobenzene
Bromoxylene
12
8
250
1
<0.5
19
3
500
430
20
12
2
14
13
12
14
16
2
1
<0.5
4
0.1
0.1
9
700
21
<0.5
2
<0.5
<0.5
<0.5
Bromoethylbenzene
Halogenated anisoles
Chloinated styrenes
Chloroanisole
Dichloroanisole
Trichloroanisole
Bromoanisole
Dibromoanisole
1
3
1
10
1
0.1
<0.1
1
0.1
Dichlorostyrene
Trichlorostyrene
Pentachlorostyrene
Hexachlorostyrene
Heptachlorostyrene
Octachlorostyrene
1
2
5
0.2
0.1
<0.5
5
Halogenated alkanes
DDT-metabolites
Anilins/phenols
1,1,2,2-Tetrachlorethane
Hexachloroethane
46
21
18
2
36
630
Hexachloro-1,3-butadiene
Pentachlorocyclopropane
Bromoform
1
22
700
12
1
450
1,2-Dibromo-1,1,2-trichloroethane
3500
DDE
DDNS
DBP
<0.5
<0.5
<0.5
<0.5
<0.5
1
DDCN
DDNU
DDM
2
Dichloroanilin
Tribromoanilin
4-Chloroionol
4-Bromoionol
2,4,6-Tribromophenol
<0.5
Diphenyl ethers
Micellaneous
Phenoxybenzene
Methylclorofen
<0.5
2
0.4
2
Chlorophenoxyanisole
Dichlorophenoxyanisole
Chloropropiophenone
Dibromoacetonitrile
3,30-Diisopropylbiphenyl
Dimethylsulfone
2
<0.5
<0.5
N-Formylpiperidine
Tetrabutyl tin
2
1
12
Tetrachlorothiophen
Tetramethyl urea
0.1
<0.1
E ¼ Extractable fraction; BBr3 ¼ after boron tribromide treatment; RuO4 ¼ after ruthenium teroxide oxidation; Pyr ¼ after pyrolysis; TCH ¼ after thermochemol-
ysis. All data are given in mg/kg.
occurred predominantly within the non-extractable fraction, re-
leased after ruthenium tetroxide oxidation with concentrations
of 15 mg/kg (M1) and 8 mg/kg (M2). Hexachloro-1,3-butadiene
was exclusively detected in the extract of sample E1 with a con-
centration of 630 mg/g. Negligible amounts were also quantified
after pyrolysis. Pentachlorocyclopropane was detected in sam-
ples M1, M2 and M3 after ruthenium tetroxide oxidation, exclu-
sively, with concentrations of up to 22 mg/kg. Bromoform was
identified after boron tribromide treatment and ruthenium te-
troxide oxidation in samples M1, M2 and M3. In sample E1,

184
A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
fraction, DBP and DDM occurred after boron tribromide treat-
ment or thermochemolysis. Based on structural properties and
its release after boron tribromide treatment, significant
portions of bound DBP are assumed to be incorporated by
ether bonds. This is in accordance with Schwarzbauer et al.
(2003a). Within the latter investigation, non-extractable
DDT-related compounds were studied in detail in highly
contaminated riverine sediments. Potential sources for such
contaminations are agricultural activities or effluents from pro-
duction plants.
Fig. 4. Proposed way of generation of bromodichlorobenzene from dichloro-
benzene incorporated by ether functionalities by BBr3-treatment. RM is an
associated organic macromolecular structure.
the compound occurred after ruthenium tetroxide treatment,
only. While the concentrations of the compound in samples
E1, M1 and M3 were up to 770 mg/kg, quantities in M2 were
only up to 4 mg/kg. 1,2-Dibromo-1,1,2-trichloroethane was
released after ruthenium tetroxide degradation in all Mulde
River samples with concentrations of up to 3500 mg/kg. Gener-
ally, concerning modes of incorporation of halogenated alkanes,
a reasonable assumption is a strong adsorptive interaction with
macromolecular matrices. All compounds described in this sec-
tion are characterized by high molar halogen to carbon ratios,
resulting in electron depleted carbon frameworks, thus activat-
ing the molecules for potential interactions with electron
donors.
1,1,2,2-Tetrachloroethane and bromoform are known or-
ganic solvents. Furthermore, bromoform is a potential trans-
formation product of other halogenated alkanes and a known
disinfection by product in drinking water treated with ozone
(Richardson et al., 1999; Squillance et al., 2004). Therefore,
potential sources can be of industrial and municipal origins.
Hexachloroethane is used as a solvent, ignition suppressant
and as a polymer additive, associating this compound to indus-
trial effluents. Hexachloro-1,2-butadiene is used for multiple
technical purposes and is a by product derived from technical
chlorochemical processes. The contaminant has been fre-
quently detected in riverine systems (Booker and Pavlostathis,
2000; Kronimus et al., 2004; Lee and Fang, 1997).
3.6. Halogenated anilines and phenols
Halogenated anilines and phenols, in particular di- and tri-
chloroaniline, 4-chloroionol (4-chloro-2,6-di-tert-butyl phe-
nol), 4-bromoionol (4-bromo-2,6-di-tert-butyl phenol) and
2,4,6-tribromophenol, have been identified in samples E1,
M1 and M2. In sample M1, dichloroanilines have been identi-
fied at low concentrations after ruthenium tetroxide oxidation
and thermochemolysis. In samples E1, M1 and M2 2,4,6-
tribromophenol was identified after ruthenium tetroxide oxida-
tion. The quantitatively most extensive load of 21 mg/kg was
determined in sample M2. Whereas dichloroaniline was de-
tected after thermochemolysis, all other considered anilines
and phenols were detected after ruthenium tetroxide oxidation.
Covalent binding of phenols and anilines by their func-
tional groups into humic substances are known phenomenons
(Park et al., 1999; Weber et al., 1996). However, concerning
the analyzed phenols, there are no hints for an incorporation
by an ether functionality with respect to the analytical results
after boron tribromide treatment. Consequently, other interac-
tion types, e.g. charge-transfer-complexation have to be pres-
ent. Regarding chlorinated anilines, a present amino-covalent
incorporation might resist attacks by boron tribromide and
might therefore be cleaved after ruthenium tetroxide oxida-
tion, only. Chlorinated anilines are known industrial by-
products or pesticide degradation products (Kristenson et al.,
2004). The detected phenols are previously described drinking
water disinfection by-products originating from ozonization
processes in presence of bromide (Richardson et al., 1999).
Potential sources of chlorinated anilines are agricultural activ-
ities as well as industrial sources. The detected compounds re-
lated to disinfection by-products can be of municipal origin.
Pentachlorocyclopropane is used as a reactant and reagent
in synthetic chemistry (e.g. Taylor et al., 1994) and therefore
represents chlorochemical industrial effluents. 1,2-Dibromo-
1,1,2-trichloroethane is used as a chain transfer agent in
PVC polymerization (Stanaback, 1977). Thus, potential sour-
ces are also procedural processes.
3.5. DDT-metabolites
Six metabolites of the pesticide DDT (1,1,1-trichloro-2,
2-bis(4-chlorophenyl)ethane), in detail DDE (1,1-dichloro-2,
2-bis(4-chlorophenyl)ethene), DDNS (1,1-bis(4-chlorophenyl)
ethane), DBP (4,40-dichlorobenzophenone), DDCN (bis(4-
chlorophenyl)acetonitrile), DDNU (1,1-bis(4-chlorophenyl)
ethene) and DDM (4,40-dichlorodiphenylmethane) were
detected in samples from the Mulde River. Whereas all
mentioned compounds occurred within the extractable frac-
tion, only DBP and DDM were identified as non-extractable
portions. The contamination can be classified as non-recent
because the parent compound DDT was not detected. Quanti-
tative analysis revealed generally lower concentrations; maxi-
mum concentration of a single metabolite was 13 mg/kg of
DDCN in sample M1 (Table 2). Within the non-extractable
3.7. Diphenylethers
Four diphenyl ethers have been detected, in detail phenoxy-
benzene, methylclorofen (2-benzyl-4-chloroanisol), chlorophe-
noxyanisole and dichlorophenoxyanisole. The quantitatively
most important diphenylether, phenoxybenzene, appeared
within the extractable and non-extractable fractions at concen-
trations levels of up to 5 mg/kg. All other detected dipheny-
lethers occurred after thermochemolysis exclusively, at low
concentrations of up to 0.4 mg/kg. The so far rarely described
chlorinated phenoxyanisoles have been identified in samples
M1 and M2, only. In sample E1, no diphenylethers have been
detected within the non-extractable fraction.

A. Kronimus, J. Schwarzbauer / Environmental Pollution 147 (2007) 176e186
185
With respect to its molecular structure, phenoxybenzene
might be incorporated by hydrogen bonds or adsorptive forces.
The obtained analytical data allows no specific classification.
Regarding the three double ethers, an interaction by ether
bonds is a reasonable hypothesis. However, incorporation
by ether bonds should be verifiable by boron tribromide
degradation. Fig. 5 illustrates four conceivable reaction path-
ways of etherically incorporated chlorinated phenoxybenzenes
during boron tribromide treatment. Therefore, possible degra-
dation products are chlorinated bromobenzenes, dibromo-
benzenes, halogenated phenols and benzenediol. While
a dichlorobromobenzene and also a dibromobenzene isomer
were identified after boron tribromide degradation, the other
products have not been detected. Consequently, the analytical
data reveals no evidence for an incorporation by ether bonds.
Also the methoxy group of methylclorofen suggests a analo-
gous mode of incorporation, however there is also no evidence
by the analytical results.
suggestion for the compound’s incorporation. An analogous
interaction type might be present during the bound state of
dimethylsulfone and N-formylpiperidine. N-Formylpiperidine
is used for several technical purposes and is therefore not
source specific (Kronimus et al., 2004). Tetramethyl urea is
an intermediate in many technical synthesis and is also, as
well as dimethylsulfone, potentially of industrial origin. Tetra-
chlorothiophen is a product of garbage incineration and a con-
stituent of fly ash (Bechtler et al., 1995; Wienecke et al., 1995)
and therefore of pyrogenic origin and indicative for atmospheric
emission. Dibromoacetonitrile is a known drinking water disin-
fection by-product (Richardson et al., 1999) and may therefore
be discharged from municipal effluents.
4. Conclusion
Within the present investigation, a comprehensive analysis
of anthropogenic organic contaminants considering extract-
able and non-extractable fractions was performed. Due to
the different qualitative composition of the two fractions, it
was demonstrated that emission sources cannot be comprehen-
sively determined by considering extractable contaminants
only. Combined application of selective sequentially per-
formed chemical degradation procedures and thermochemical
degradation approaches elevated the quality of information.
Quantitative analyzes demonstrated comparable amounts of
contaminants within the extractable and non-extractable
fraction.
A structure related interpretation of the detected com-
pounds revealed by the different degradation methodologies
allowed insights into compound specific modes of incorpora-
tion of several xenobiotics. Considering chlorinated benzenes,
the analytical results indicated a dependence of the present
mode of incorporation on the substitution pattern. Thermoche-
molysis treatment revealed so far rarely reported chlorinated
phenoxyanisoles. Their structural properties suggest their in-
corporation by an ether functionality, however results obtained
by boron tribromide treatment do not support this hypothesis.
Furthermore, several compounds, in particular chloropropio-
phenone, diisopropylbiphenyl and tetrabutyl tin seem to have
very poor tendency for incorporation.
Phenoxybenzene is used for several technical purposes, for
example as an antioxidant in rubber, as a stabilizer in perfume
and soaps and as a herbicide and is therefore not source spe-
cific (Heim, 2005). Methylclorofen, a derivate of clorofen,
which is used as an antiseptic, was potentially emitted by mu-
nicipal effluents.
3.8. Miscellaneous compounds
Chloropropiophenone, diisopropylbiphenyl, and tetrabutyl
tin occurred within the extractable fraction, only. The remain-
ing compounds were detected exclusively as bound residues.
Chloropropiophenone, the PCB substitute diisopropylbiphenyl
and tetrabutyl tin seem to have no or very poor affection for
incorporation. Potential sources are clearly industrial effluents
(Kronimus et al., 2004; Peterman and Delfino, 1990).
Although the carbonyl function of tetramethyl urea suggests
an incorporation by ether bonds, analytical results of boron tri-
bromide treatment debars this. Interaction with free electron
pairs located at the oxygen and nitrogen atoms is a reasonable
Within further corresponding research, more case studies
will have to be performed for expanding and systematizing
the database. Additionally, the phrased hypotheses considering
compound specific incorporation modes have to be evaluated
within long-term laboratory experiments.
Acknowledgement
We gratefully acknowledge the financial support by the
German Research Foundation (DFG).
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