Science of the Total Environment 408 (2010) 5147–5157

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Science of the Total Environment

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s c i t o t e n v

Municipal landfill leachates: A significant source for new and emerging pollutants
Trine Eggen a,⁎, Monika Moeder b, Augustine Arukwe c
a
Bioforsk, Vest Særheim, Norwegian Institute for Agricultural and Environmental Research, Postveien 213, N-4353 Klepp st., Norway
b
Helmholtz Centre for Environmental Research UFZ, Department of Analytical Chemistry, Permoserstrasse 15, D-04318 Leipzig, Germany
c
Department of Biology, Norwegian University of Science and Technology (NTNU), Høgskoleringen 5, 7491 Trondheim, Norway

a r t i c l e i n f o a b s t r a c t

Article history: Landfills have historically remained the most common methods of organized waste disposal and still remain
Received 22 April 2010 so in many regions of the world. Thus, they may contain wastes resulting from several decades of disposal
Received in revised form 15 July 2010 and decomposition with subsequent release of organic compounds that may have environmental, wildlife
Accepted 17 July 2010
and human health consequences. Products containing different types of additives with unique beneficial
Available online 8 August 2010
improvement properties are in daily use. However, when these products are decomposed, additives are
Keywords:
release into the environment, some of which have been shown to have negative environmental impacts,
Landfill leachates resulting in the ban or at least restricted application of some chemicals. New and emerging compounds are
Pharmaceuticals continuously discovered in the environment. Herein, we report qualitative and quantitative data on the
Musk compounds occurrence of new and emerging compounds with increasing environmental and public health concern in
Perfluorinated compounds water- and particle phase of landfill leachates. Under normal environmental conditions, several of these
Non-target screening chemicals are persistent high-volume products. Identified chemicals in the leachates at nanogram (ng) or
microgram (μg) per liter levels include — chlorinated alkylphosphates such as tris(1-chloro-2-propyl)
phosphate (TCPP), N-butyl benzensulfonamide (NBBS), the insect repellent diethyl toluamide (DEET) and
personal care products such as the non-steroidal anti-inflammatory drug ibuprofen and polycyclic musk
compounds. Among new and emerging contaminants, perfluorinated compounds (PFCs) were measured in
the water phase at concentrations up to 6231 ng/L. Compared with the other chemicals, PFCs were primarily
distributed in water phase. An effective removal method for PFCs and other polar and persistent compounds
from landfill leachates has been a major challenge, since commonly used treatment technologies are based
on aeration and sedimentation. Thus, the present study has shown that municipal landfill leachates may
represent a significant source of concern for legacy, new and emerging chemicals in groundwater.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
Municipal landfills may be sources of a wide range of compounds
with environmental, wildlife and human health concern. Several studies
have been performed in order to understand the chemical processes in a
landfill and identifying potentially environmentally hazardous com-
pounds in leachates (Paxéus, 2000; Schwarzbauer et al., 2002; Öman
and Hynning, 1993). In recent decades, the content of wastes in landfills
has changed, mainly as a result of higher demand and better quality of
consumer products. For example, batteries, paints, oils, electrical
products and pharmaceuticals that are potentially deposited at landfills
contain additives that might have a negative impact on environmental
and human health. Flame-retardants, plasticizers, surface-active sub-
stances and fragrances are chemicals commonly used to improve certain
properties of consumer products. Previous studies on landfill leachates
have evaluated parameters such as organic matter, chemical- and
⁎ Corresponding author.
E-mail address: Trine.Eggen@bioforsk.no (T. Eggen).
biological oxygen demand, nutrients and metal ions. Since the 1990s,
extended studies that include organic chemical groups such as phenolic
compounds, aromatic acids, chlorinated aromatic compounds, and
polycyclic aromatic compounds, have been reported (Paxéus, 2000;
Schwarzbauer et al., 2002; Welander, 1997; Öman and Hynning, 1993).
New and emerging groups of compounds such as perfluorinated
compounds (PFCs), are now detectable in most environmental matrix
(Schultz et al., 2006; Sinclair and Kannan, 2006; Woldegiorgis et al.,
2006) and in biota (Kannan et al., 2002; Martin et al., 2004).
Particularly, perfluorooctane sulfonate (PFOS) and perfluorooctanoic
acid (PFOA) have received attention because of their unique
chemistry (as both water and oil repellent and reduction of surface
tension), persistence, bioaccumulation and toxic effects. Thus, PFCs
have a widespread application in a myriad of products, including
household cleaning agents, carpets, textiles, paper coatings, cos-
metics, fire-fighting foams and packaged-food containers (Hekster et
al., 2003). Presently, few data on landfill leachates have been reported
showing that these may represent a significant source of PFCs (Bossi
et al., 2008; Kallenborn et al., 2004; Woldegiorgis et al., 2006; Busch et
al., 2010). Contrary to many persistent organic pollutants with a

0048-9697/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2010.07.049
5148 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157
medium to high hydrophobicity, many PFCs are mainly found in the
water phase (Schultz et al., 2006; Woldegiorgis et al., 2006), and
efficient removal of these compounds becomes a challenging task
during leachate treatment. Many municipal landfills discharge
directly into waste water treatment plants (WWTPs) without
treatment, resulting to environmental spreading of PFCs, polar and
persistent emerging compounds such as N,N-diethyl toluamide
(DEET), alkylphosphates, pharmaceuticals and personal care products
(PPCPs).
Recently, a wide range of PPCPs has been detected in the
environment (Kolpin et al., 2002; Rimkus, 1999). Domestic pathway
through municipal sewage treatment plants (STPs) has been
recognized as the main route of human pharmaceutical substances
into the aquatic environment (Ternes, 1998). Polycyclic musk
substances are active ingredients in cosmetics and household
products that are used worldwide in large quantities and subse-
quently ending up in landfills (Salvito, 2005). For example, 1,3,4,6,7,8-
hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran
(HHCB or Galaxolide®) and 6-acetyl-1,1,2,4,4,7-hexamethyltetraline
(AHTN or Tonalide®) seem to represent the most abundant musk
fragrances in the environment that potentially accumulate in sewage
sludge (Mogensen et al., 2004). Many of the emerging compounds
with suspected risks to organisms and human health include, the
insect repellent, DEET (Corbel et al., 2009). Although most of these
compounds are present at trace levels in the environment, harmful
effects to the ecosystem and to the food web cannot be excluded.
Persistent drugs such as carbamazepin, is not effectively removed
from wastewater and may therefore enter, at least, the aquatic
environment with unknown implications (Andreozzi et al., 2002;
Isidoria et al., 2005; Zurita et al., 2007). Regulatory consequences on
the risks associated with the presence of these compounds in the
environment have been the subject of continuous discussion for
decades (Ternes, 2001).
The aims of the present were, firstly to investigate the levels of
emerging organic compounds in untreated landfill leachates using a
non-target full scan screening analysis (landfill A, B and C) and
secondly perform quantitative analysis of selected PPCPs (landfill A)
and PFC (landfill B and C). In order to get an overall knowledge about
the distribution patterns and suitable treatment processes for
removing such compounds in untreated leachates, the quantification
of emerging compounds were performed separately in water- and
particle phases.
2. Materials and methods
2.1. Leachate sampling
Three differently engineered landfills are included in this study.
Landfill A is located in an abandoned sand/gravel pit without bottom
liner. The bottom of the old part of the landfill is approximately at the
groundwater level and the landfill is further limited to the east and
north by solid bedrock, granite gneiss. The landfill is limited on the
Westside by a ridge of massive rock, overlaid by a thin layer of compact
moraine, sand/gravel and locally marine clay. Leachate from this site
enters the groundwater through the sand/gravel aquifer and follows a
well-defined path to a concentrated spring located 200 m downstream
before a treatment system containing an aerated lagoon and a wetland
filter. Five leachate samples were collected at and downstream of
landfill A; i) a well located just below the old landfill site (W-old), ii) a
well in the lower part of the currently active landfill (W-active), iii and
iv) wells located 50 (W-50) and 100 (W-100) downstream of the
landfill, respectively, and v) inlet water to the treatment system, taken
in the pumping house, 200 m downstream of the landfill (W-200)
(Fig. 1). Both landfills B and C had clay liners and a tubing system for
collecting leachates and a direct discharge of the leachates without
treatment to the municipal wastewater net. Groundwater (W-old, W-
active, W-50 and W-100) for non-target screening was sampled with
the use of a peristaltic pump with Teflon tubing. The samples were
pumped into autoclaved acidified (10 mL 3 M H2SO4) N2-purged 1-liter
glass flasks. Leachates from landfills B, C and W-inlet at landfill A, were
sampled directly into pre-prepared 1 L sampling bottles. Non-target
screening samples and quantitative PPCP analysis were sampled in glass
bottles while samples for quantitative PFC analysis was sampled into
methanol washed PE quality plastic bottles. The flasks were filled
completely and stored in dark conditions, at 4 °C until analysis.
Information on the landfills is summarized in Table 1.
2.2. Non-target screening and target analysis of selected emerging
compounds
Qualitative screening for organic compounds were performed only
with leachates from landfills A, B and C. Sample preparation by solid
phase extraction (SPE) was performed essentially as previously
described by Braun et al. (2003). Briefly, 1-L of each water sample
was filtered and thereafter Soxhlett-extracted with toluene. From a
final volume of 500 μL, a 1 μL aliquot was analyzed by GC-MS. The
water samples (adjusted to pH 3 and spiked with the internal
standard) were extracted by SPE on a mixed sorbent bed (LiChrolut®
EN and LiChrolut® C18; both from Merck, Darmstadt, Germany) and
eluted with acetone. A cleanup on silica gel accomplished the sample
preparation prior GC-MS analysis. A GC-MSD instrument (6890 HP-
MSD; Agilent Technology, Waldbronn, Germany) equipped with a
30 m HP-5MS capillary (0.25 mm I.D., 0.25 μm film) was used for
analysis. Full scan mode (50–500 amu) was applied for qualitative
screening (non-target analysis) and selected ion monitoring (SIM)
mode for quantification of selected emerging substances. The
carboxylic drugs were analyzed after derivatization with GC-negative
chemical ionization mass spectrometry in accordance to Möder et al.
(Möder et al., 2007). Quantitative analysis of the PPCPs, were
performed with samples from landfill A and the limits of quantifica-
tion (LOQ) are specified in Table 4.
2.3. Determination of ionic perfluorinated substances and telomers
Quantitative analyses of PFCs in water- and particle phases were
performed for leachates from landfills B and C, and sediment samples
from landfill D. All sampling devices were free of perfluorinated
polymers to avoid cross-contamination. About 2 g of dry sample was
spiked with 20 μL internal standard, 13C PFOS and 13C PFOA (0.5 ng/
μL). 1 mL of 200 mM NaOH in methanol was added and soaked for
30 min. Then, 100 μL 2 M HCl in methanol was added followed by
another 9 mL of methanol. The mixture was thoroughly mixed and
then extracted on a wrist-action-shaker for 30 min. After centrifuga-
tion (2000 rpm, 5 min), 1 mL of supernatant methanol extract was
treated with 25 mg ENVI-Carb mixed in 50 μL glacial acetic acid. After
thorough mixing and centrifugation (10,000 rpm, 10 min), 20 μL
recovery standard, 0.1 ng/μL 3,5-bis(trifluoromethyl)phenyl acetic
acid, and 0.5 mL of 4 mM NH4 OAc in water were added to the final
extract prior to analyses by the HPLC/MS system (binary pump 1525 μ
with a Waters 2777 Sample Manager coupled to a Micromass (Q)-
TOF-MS (QTOF micro)).
2.4. Determination of fluorotelomer alcohols
Wet sediment samples were spiked with internal standard, 7:1 FA
(7:1 fluorinated alcohol, 98% purity) (ABCR Karlsruhe, Germany), and
extracted with ethyl acetate three times for 30 min on a wrist-action
shaker. Centrifugation and cleanup on ENVI-Carb was performed as
described above, without the addition of glacial acetic acid. Recovery
standard, 1,2,3,4-tetrachloronaphthalene (1,2,3,4-TCN, 10 μg/mL in
isooctane) (Dr.Ehrenstorfer, Augsburg, Germany), was added prior to
 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157 5149

Fig. 1. Map of landfill A showing the study wells. W-old = from closed and vegetated part; W-active = from the active part, W-50 and W-100 are approximately 50 and 100 m
downstream, respectively, and W-inlet is inlet to treatment plant.

GC-MS analysis (GC-MS: 7890A GC split/splitless injector coupled to a
5975C MSD, Agilent, Böblingen, Germany).
3. Results and discussion
3.1. Non-target screening of organic compounds
Organic compounds identified by GC-MS full scan analysis of
leachates from landfills A, B, and C was classified into substance groups
to facilitate interpretation of leachate composition. The non-target
analysis indicated hundreds of compounds per sample and about 80%
could be classified into substance groups. Thus, qualitative and semi-
quantitative overviews on the substances released and transported via
the leachates (Fig. 2) were obtained. However, their assignment to
compound classes allowed a qualitative and semi-quantitative overview
of the substances released and transported via the leachates (Fig. 2). A
comprehensive list of identified compounds is provided in Table 2.
Identification of chemicals in the landfill and their transport down-
stream of a sandy aquifer were studied in detail at landfill A (Fig. 1). A
sample from 200 m downstream (or W-inlet) is the influent to the
treatment system. Samples from landfills B and C were untreated
leachates taken at the point of discharge to wastewater treatment
drainage. Based on GC peak comparisons in the analyzed samples,
leachates from landfill B proved to contain the highest level of total
organic compounds (Fig. 2A). The total organic loads of leachates from
landfills B and C were approximately 4 and 1.5 times higher than those

Table 1
Summarized information about the investigated landfills.

Landfill App. leachate volume [m3/year] Estimated waste deposited [volume m3] Opened-closed Waste description

A 58,000 Old part: 20,000 1973–1989 Domestic and general industrial waste
Active part: 6000 1985→ Separated residual domestic waste
B 345,000 1 300,000 1974–2006 Domestic and general industrial waste
C 124,300 450,000 1972–2002 Domestic and general industrial waste
5150 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157

Fig. 2. Distribution of organic compound groups identified in leachates from landfill A (investigated in 2002); landfills B and C (analyzed 2006). Results are base on GC peak areas of
the GC-MS full scan analysis. A shows the total content of organic compounds, while B shows relative distribution of compound groups. Alternative 1: For description of samples at
landfill A, please see text for Fig. 1. Alternative 2. W-old = closed and vegetated part; W-active = from the active part; W-50 and W-100 approximately 50 and 100 m downstream,
respectively, and W-inlet is inlet to treatment plant.

from landfill A (W-active), respectively. At landfill A, leachate of the
fresh active part releases about 10-fold more organic substances than
leachate from the old, inactive dump (W-old — Fig. 2A). The amount of
organic substances decreased in the wells downstream of the landfill,
although W-100 is at the same level as W-active (Fig. 2A).
In addition to variation in the total content of organic compounds,
the composition of pollutant mixtures were different at sites A, B, and C,
and also between samples at landfill A (Fig. 2B). The ratio of PAHs to
cycloalkanes, alkanes, and iso-alkanes may indicate the degradation
potential in landfills. The preferred biodegradation sequence between
these groups of compounds has been discussed in many studies
(Leahy and Colwell, 1990; Prince, 1993). Although not a universal
pattern, a frequently found degradation pattern is unbranched
alkanes N branched alkanes N low-molecular-weight aromatics N
cycloalkanes and high-molecular-weight polycyclic aromatic hydro-
carbons (PAHs). The semi-quantitative pattern of organic substance
groups in the leachates may be used as a fingerprint in characterizing
landfills with regard to age of waste deposit, type of waste or
biodegradation potential. The highest proportion of alkanes was
measured in leachates from landfill C and in W-50 at landfill A. In
general, these indicate different sources of waste and probably different
biodegradation potential in the landfills. The proportion of cyclic or
unsaturated hydrocarbons was high in leachates from landfills B and C.
The phthalic acid esters-bis(2-ethylhexyl)phthalate (DEHP), dibutyl
phthalate (DBP), and diethyl phthalate (DEP) (grouped as benzenedi-
carboxylic acid esters and contributing 5–20%) were detected in at least
three leachate samples at all landfills (Table 2). Methylated phthalates,
used as solvent in perfumes and pesticides, were identified in leachate
from active parts of landfill A and landfills B and C. Phthalates has been
detected in leachates from landfills in several studies (Paxéus, 2000;
Schwarzbauer et al., 2002; Welander, 1997; Öman and Hynning, 1993),
and DEHP in the range of 97,000–346,000 ng/L (Paxéus, 2000).
Alkylated phosphates, both chlorinated and non-chlorinated, were
found in all leachate samples (approx. 2–10% of total organic
compounds) and triethylphosphate and tris(chloropropyl)phosphate
(TCPP) were detected in all leachates samples, except in the W-active
of landfill A (Table 2). Tri(2-chloro-ethyl)phosphate (TCEP) and TCPP,
along with other trialkylphosphates, have been previously reported in
landfill leachates (Barnes et al., 2004; Paxéus, 2000; Schwarzbauer et
al., 2002). TCEP, TCPP and Tri-iso-butylphosphate have been reported
in respective ranges of 220–240,000, 4000–50,000 and 110,000–
350,000 ng/L (Barnes et al., 2004; Paxéus, 2000; Schwarzbauer et al.,
2002).
The insecticides, N,N-diethyl toluamide (DEET), benzothiazole,
and N-butyl benzenesulfonamide (NBBS), are widely used chemicals
in industry and household products, thus their occurrence in all
leachate samples from landfills A, B, and C were in accordance with
previous studies that detected these compounds in landfill leachates
(Barnes et al., 2004; Paxéus, 2000; Schwarzbauer et al., 2002;
Welander, 1997). The polar properties of these substances with
respective log Kow values of 2.2, 1.99, and 2.1 (Westerhof et al., 2005),
contribute to their spread in aqueous environment (Barnes et al.,
2004; Schwarzbauer et al., 2002; Öman and Hynning, 1993). For
example, while NBBS is a naturally occurring substance that is used
commercially as plasticizer in the polymerization of polyamides and
has previously been shown to be neurotoxic (Strong et al., 1991),
DEET is an insect repellent protecting against mosquitoes and whose
widespread use is reflected on the frequent detection in leachates at
μg/L concentration level. Bacterial transformation of DEET in test
cultures has been reported (Rivera-Cancel et al., 2007), but data on its
 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157 5151

Table 2
Organic compounds detected in leachates from landfills A, B and C, compared to literature data.

Landfill A Landfill Landfill

W-old W-active W-50 W-100 W-inlet B C Literature

Aliphatic alcohols and ethers Leachates composition of these general groups of

Diethoxy methane + organic compounds (a,b,c,d)
Trimethoxypentane +
Methoxy-isopropoxy propanol +
Methoxyethanol + + +
Dimethyl decalol +
Vinyl-ethyl carbitol + +
Aldehydes and ketons
Cyclohexadiene-1,4-dione +
C3-benzaldehyd +
C5-cyclohexanone + + +
C2-heptadienone + + +
Alkyl dihydrofuranone +
Benzophenone +
Aliphatic acids and esters
Propanic acid + + + +
Dodecanoic acid +
Tetradecanoic acid + + + + + +
Pentadecanoic acid + + + + +
n-Hexadecanoic acid + + + +
Octadecanoic acid + + + +
Trimethyl hexanoic acid + +
Tridecanoic acid + + +
Hexadecanoic acid, ethylester + + + +
Aromatic carboxylic acids and esters
C2-benzoic acid + + + + + +
C3-benzoic acid + + + + +
C3-benzoic acid ethylester + +
C4-benzoic acid +
Bis(tert-butyl) benzoic acid + + + +
Benzoic acid (phenylmethyl + +
ester)
Phenylacetic acid, ethyl ester +
C2-phenylacetic acid +
3,5-bis(iso-butyl)benzoic acid +
tert-Butyl benzoic acid + + +
Iso-propylphenylacetic acid + + + +
p-tert-butyl benzoic acid + +
Methoxy-phenyl-octanyl-propionic +
acid
Phenylpentenoic acid +
Dichloro benzoic acid + + + + (+) +
Methylcinnamic acid +
Polyaromatic hydrocarbons + substituted PAHs
Methyl indane + + +
Methyl tetralene +
Dimethyl tetralene +
Naphthalene + + + + + + +
Methyl naphthalene + + + +
Dimethyl or ethylnaphtalene +
Naphthalene. carbocyclic acid + + +
Acetyl-6-methoxy-naphthalene +
Biphenyl, bis(1-methyl) +
Phenanthrene, tetrahydro- + + +
Phenanthrene, methyl-(methylethyl) + + +
Trimethyl phenanthrene + +
Phenanthrene carboxyl acid +
Antracene, tetrahydro- +
Partially hydrated PAH (mw 258) + + +
Partially hydrated PAH (mw 272) + + +
Partially hydrated PAH (mw 302) + + +
Terpenoids
Camphor + + + +
Terpenic compound + + + + + +
(limonene, pinene)
Phthalic acid esters Phthalates: (a,b,d,e,f). DEHP:97–346 μg/L (a)
Methylphthalate + + +
Dimethyl phthalate +
Diethyl phthalate, + + + + + +
Dibutyl phthalate + + + + +
Bis(2-ethylhexyl)phthalate + + + + + +
(DEHP)
(continued on next page)
5152 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157

Table 2 (continued)
Landfill A Landfill Landfill

W-old W-active W-50 W-100 W-inlet B C Literature

Phosphoric acid derivatives Organophosphates: (a,b,c,e,) TEP: 40–110 μg/L (c),

Ethanol, 2-butoxy-, phosphate + TCPP:4–50 μg/L (a)
Phosphoric acid ester + + +
Chlorinated phosphoric acid ester + + +
Ethyl-phosphoric acid dietylester +
Triethyl phosphate (TEP) + + + + + +
Tris(chloropropyl) phosphate + + + + + +
(TCPP)
Phenolic compounds Leachates composition of these general groups
C2 phenol + + + of organic compounds (a,b,c,d)
C3 phenol + + +
C4 phenol + +
Di-tert-butylphenol (antioxidant) + + + + + +
Di-tert butyl-hydroxylphenyl +
propoinic acid
2(2-OH-phenyl)-2,5 +
cyclohexadiene-1,4-dione
Phenol, 4-chloro-2-methyl- +
Benzene derivatives
C2-benzene + + +
C3-benzene + + + +
C4-benzene + + + + + +
Bis(methylethyl)benzene + + + +
Methoxy-benzeneproponol + + +
Trimethoxy benzene +
Alkanes and cycloalkanes
Alkanes + + + + + + +
Cycloalkanes + + + + + + +
Steroides
Cholestene + + +
Cholestendien + + +
Cholestanone + + +
Megastigmatrienone + + +
Vitamine
Tocopherol + + +
Benzthiazoles Benzathiazole:0.4–2 μg/L (a)
Benzothiazole + + + + +
Benzothiazolone + + + + + (+)
Pesticidecides
Bentazone (herbicide) + + +
N-containing compounds N-containing: (a,c), DEET:5.5–320 μg/L (b,c)
Methylphenyl acetamid
C4 pyridinium derivative
Diethyl toluamide (DEET)
S-containing compounds S-containing: (a,c)
Dimethyl thiophane +
Propyl thiophane +
Thiophene derivative + + +
Di isobutylthiophene +
Thienyl benzoic acid ethyl ester +
Octaatomic sulfur + + + +
Sulfonamides Sulfonamides and NBBS: 0.7–710 μg/L (a,c,d)
Benzensulfonamide +
N-butyl benzenesulfonamide (NBBS) + + + + + +
(N-ethyl-4 methyl) + + +
benzenesulfonamide
Drugs and metabolites Pharmaceuticals: (b,c,g)
Non-steroidal inflammatory drug (+)
Phenylbutazone +
Metabolite of analgetic drug
Propylphenanzone + +
Anti-infective agent
Crotamiton + +

(+) Interferred peak.

mw Molecular weight.
a) Paxéus, 2000, b) Barnes et al., 2004, c) Schwarzbauer et al. 2002; d) Welander 1997, e) Öman and Hynning, 1993, f) Bauer and Herrmann, 1998, g) Holm et al., 1995.

environmental fate are scarce. Biodegradation of alkylated benza-
mides and benzenesulfonamides under anaerobic conditions have
been previously studied showing the absence of DEET degradation
during an 11 months period (Kuhn and Suflita, 1989). NBBS has also
been measured in landfill leachates at μg/L range (Paxéus, 2000;
Schwarzbauer et al., 2002; Welander, 1997) and standardized OECD
tests have classified this compound as persistent. Considering the
polarity of TCPP with log Kow 2.59–3.33 (OECD), TCEP with log Kow 1.4
(Westerhof et al., 2005), DEET and NBBS (see above), these chemicals
are not expected to bioaccumulate in the environment, although their
persistence and high polarity render them potentially readily
transportable through conventional landfill treatment systems.
Table 3
PFCs analysis of untreated leachates, separatly water- and particle phases given in ng/L, from landfills B and C. Ranges and average concentrations in landfill leachates and sediment from treatment systems (given in ng/g d.w.) from other
studies from the litterature is presented.

Units Landfill B Landfill C Landfill data. Field et al. 2005a1 Landfill data Kallenborn Landfill data Landfill data Landfill data
et al. 2008b Bossi et al. 2008c Busch et al. 2010d1 Woldegiorgis et al. 2006e

T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157

Water Particle Water Particle Water Particle Sediment Watera2 Sedimenta2 Water Water Water Water

ng/L ng/L ng/L ng/L ng/L ng/L ng/g d.w. ng/L ng/g d.w. ng/L ng/L ng/L ng/L

PFBS b5 b LOD b5 b LOD bLOD-4 b LOD-19.7 0.06–1.522 b 100 b 0.0004 5.64–112 (51.5) n.a. b0.39–1356 (220) b0.5–110 (37.3)
PFHxS 281 0.15 89 0.05 5.6–40.67 0.1–14.6 0.101–0.489 100 0.894–1.1 12.4–143 (77.0) b0.2–3.1 b0.24–178 (22.2) 12–1800 (518)
PFOS 2920 33.9 455 7.28 4.2–24.2 1.0–9.4 0.216–10.02 300 23.6–254 32.8–187 (82.5) b0.5–3.8 (1.1) 0.01–235 (30.9) 32–1500 (555)
PFDcS b 14 b LOD b14 b LOD bLOD-0.03 b LOD-0.03 b LOD b2 0.431–0.6 n.a. n.a. n.a. b1–0.28 (0.07)
PFBA b185 b LOD b 185 b LOD n.a. n.a. n.a. b50 b 0.041–22.0 n.a. n.a. b3.36–2968 (458) b12–30 (7.5)
PFHxA 757 b LOD 590 b LOD bLOD-60.8 b LOD-19.6 0.271–2.718 100 b 0.032–2.6 26.4–697 (228) n.a. b0.37–2509 (234) b7–310 (77.5)
PFHpA 277 b LOD 215 b LOD bLOD-21.4 0.6–7.7 0.04–0.538 b60 b 0.002–2.4 n.a. n.a. b0.12–280 (48.1) b20–260 (197.5)
PFOA 767 4.05 532 2.76 23.2–115.6 5.8–157.2 b LOD-7.862 300 6.4–23.7 92.4–516 (293) b2–5.8 (2.9) b0.40–926 (145) 38–1000 (537)
PFNA 539 b LOD 310 b LOD bLOD-1.1 b LOD-2.7 b LOD-0.562 b 0.002–1.43 4.7–61.5 (34.8) b0.8 b3.63–80.1 (7.29) b18–100 (43.5)
PFDcA b 75 b LOD b75 b LOD n.a. n.a. n.a. b10 0.9–9.07 n.a. b1.6 b0.21–55.1 (5.98) b20–220 (82.5)
PFUnA b 29 b LOD b29 b LOD n.a. n.a. n.a. b20 b 0.001–1.75 n.a. b2.2 b0.11–2.98 (0.36) b59
PFDoA b 25 b LOD b25 b LOD n.a. n.a. n.a. b10 b 0.0007–1.13 n.a. n.a. n.a. n.a.
PFOSA b 50 0.33 b50 0.44 bLOD-0.03 b LOD-0.1 b LOD b3 1.1–71.95 bLOD-3.28 (1.17) b0.3 b0.15–14.0 (2.77) b2–7 (2.75)
N-EtFOSA b 15 b LOD b15 b LOD n.a. n.a. n.a. b20 b 0.003–2.1 n.a. n.a. n.a. n.a.
6:2 FTS 582 b LOD b82 b LOD n.a. n.a. n.a. b20 b 0.018 n.a. n.a. n.a. 19–2000
6:2FTUCA b 80 b LOD b80 b LOD n.a. n.a. n.a. b 100 b 0.001–14.9 n.a. n.a. n.a. n.a.
f
Sum PFCs 6123 38.43 2191 10.53 62–251 9–227 2.78–23.54 800 381.65 31–12819d2

n.a. = not analyzed, bLOD = values were below the level of detection (LOD) which was recalculated from ng/kg particles to ng/L water sample. For data from other publication these values were not available for recalculation.
a1
A survey performed in Norway 2004. Untreated leachates from six landfills. Samples were filtrated but pore size not given. LOD in the range 0f 0.02–0.1 ng/L in water samples, in the range of 1.8–106.35 pg/g for particles and sediment.
a2
Two supplementary sediment samples and one water sample at landfills same as included in the study of Field et al. 2005. Sampled in 2006.
b
Data from 5 Landfills. Samples filtrated (GFF 142 mm. PALL Life Sciences, NY cat no 61635). Both untreated and treated leachates.
c
Data from two landfills: Samples filtrated, pore size not given.
d1
A study with 22 landfills where both untreated and treated leachates were analyzed. In the table sum PFC of untreated leachates is presented. Samples filtrated b 1.2 μm.
d2
Sum PFC of untreated leachates, n = 4, is presented.
e
Data from 4 landfills. Samples not filtrated. Treated leachates. One untreated leachate sample was analyzed but showed extremely high levels and not included.
f
PFCs analyzed for in our samples which were below LOD: PFPA, PFTrA, N-Me-FOSE, N-Et-FOSE, N-Me-FOSA, 4:2 FTOH, 6:2 FTOH, 8:2 FTOH, 10:2 FTOH, 8:2 FTS, 8:2 FTUCA. FTOH LOD in the range of 0.007–0.099 ng/g.

5153
5154 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157
3.2. Quantitative analysis of compounds
Selected PFC and PPCP substances classified as emerging con-
taminants and predicted to be in leachates were quantified.
3.2.1. PFC
The PFC data presented in present study were sampled in 2006. A
presentation and discussion of this data (our data), Norwegian data from
2004 (Fjeld et al., 2005) and other published data from other countries
(Busch et al., 2010; Kallenborn et al., 2004; Woldegiorgis et al., 2006) is
presented in Table 3 and will be discussed in the proceeding sections.
The concentrations of PFCs measured in 2006 were generally higher
compared to 2004, where the majority of PFCs were found in the water
phase. In the 2004 leachates, PFOA was the predominant compound
with concentration respective ranges of 23–118 and 5.8–157 ng/L in
water- and particle phase. Concentrations of PFOS and perfluorohexane
sulfonate (PFHxS) in water- and particle phase were in the same range
of 0.1–40.7 ng/L. Perfluorohexanoic acid (PFHxA) and perfluorohepta-
noic acid (PFHpA) were detected in most samples; PFHpA in water
phase: b0.05–21.4 ng/L and particle phase: 0.6–7.7 ng/L and PFHxA in
water phase: b0.05–60.8 ng/L and particle phase: b0.05–19.0 ng/L.
Perfluorononanoic acid (PFNA) was detected only in a few samples in
2004 and highest measured value was 2.7 ng/L. In leachates from
landfills B and C, the concentrations of PFOA and PFOS in the water
phase were in the respective range of 590–757 ng/L and 455–2920 ng/L,
and showed a shift in higher concentration of PFOS than PFOA. A similar
trend was observed in the particle phase, showing a respective 2–4 and
7–34 ng/L for PFOA and PFOS. The PFOS/PFOA ratio in 2006 leachate
samples was in the range of 0.9–8.4 versus 0.05–0.4 for 2004 samples.
PFNA was detected in all water phase samples in the range of 30–
539 ng/L in 2006. Perfluorooctane sulfonamide (PFOSA) and perfluor-
butane sulfate (PFBS) were also analyzed, and were only detected in few
samples and at low concentrations (maximal values 3 and 20 ng/L,
respectively). The 2006 analysis included PFCs that were not analyzed in
2004 such as perfluorodecanoic acid (PFDcA), perfluoroundecanic acid
(PFUnA), perfluorododecanic acid (PFDoA), alkyl fluorooctansulfon
alcohols, telomer alcohols and fluortelomer sulfonates. Of these PFCs,
only 6:2 fluorotelomer sulfonates (FTS) was detected in water phase at
582 ng/L, in leachates from landfill B.
Some PFCs (combined water- and particle phase) in untreated
leachates from Norwegian landfills was in the range of 65–360 ng/L
(average 167 ng/L) in 2004 and in the range of 187–6134 ng/L (average
3085 ng/L) in 2006. For example, in a recent study by Busch et al. (2010),
the sum PFC was in the range of 31–12,819 ng/L (average 5777 ng/L) in
untreated leachates, 15–129 ng/L (average 42 ng/L) in reverse osmosis
treated leachates, 9–4079 ng/L (average 723 ng/L) in active carbon-
treated leachates (n = 8), 621 and 1257 ng/L (n = 2) in nanofiltrated
leachates, 1992 and 4610 ng/L in wet air oxidation treated leachates,
and 4023 and 8059 ng/L in biologically treated leachates. When these
values are compared for individual PFCs, our data presented in Table 3
and from other reports, there is a relatively similar pattern of
occurrence. In addition, the higher concentration of the low-chain
compounds PFBS and PFBA, long-chain perfluorinated acids (PFNA to
PFUnA) and PFOSA in the study by Busch et al. (2010), compared to
other studies. This might be related to the dominance of treated
leachates in their data set, which might change the distribution of PFCs.
Compounds not observed or seldom found in leachates (PFBS,
PFBA, long-chained PFCs, PFOSA, 2-N-ethyl-perfluorooctane sulfona-
mid (N-EtFOSA), 6:2 fluortelomer-unsaturated carboxylic acid (6:2
FTUCA)) were detected at relatively high concentrations in some
sediment samples (PFOSA 72 ng/g d.w., PFBA 22 ng/g d.w. and PFDcA
9.07 ng/g dry weight (dw)) in the present. In suspended particulate
matter in river samples, PFOSA and PFOA showed the highest
concentration in a study by Ahrens et al. (2009). The concentration
of total PFCs ranged from 1.3 to 382 ng/g dw in sediments (average
60.6 ng/g dw). The highest total PFC load was measured in leachates
from landfill C (sampled at the point of discharge to the wastewater
treatment drainage system), showing sum PFCs in the water- and
particle phases at 6123 and 11 ng/L, respectively. Based on estimated
annual loading of the leachate from the landfill (given as m3/year) and
assuming constant flow load, an approximate calculation of sum PFC
discharge from landfill B is 2.1 kg PFCs/year (5824 mg/day).
Over time, deposits of textiles, carpets, and other PFC-containing
products in landfills will decompose and release PFCs. This might be
due to release of residuals of free chemicals not linked to the polymeric
materials or excision at the polymer linkage releasing compounds such
as fluoroalcohols from the fluorinated polymers and surfactants that
are the dominant commercial and consumer utilized chemicals.
Perfluorinated phosphonic acids are an example of a recently detected
class of PFC that seems to be the precursor for PFCAs (D'eon et al.,
2009a; 2009b). Perfluorinated acids such as PFOA, PFNA, PFDcA are
used as processing aids in certain polymerizations processes, and
subsequently present in consumer products as un-reacted residual
materials. The widely used PFOS and other PFOS-based compounds
have been phased out and PFBS has been used increasingly as a PFOS
substitute. FTS are surface-active compounds mainly used in fire-
fighting foams, detergents, or in surface treatment, including house-
hold cleaning agents. Fluorotelomer alcohols (FTOH) and perfluor-
ooctane sulfonamide ethanols (PFOSE) that are the end products of
telomerization or electrochemical fluorination, respectively, are used
in the synthesis of various fluorosurfactants. The presence of these
compounds in the environment may result from the release of
residuals of free chemicals not linked to the polymeric material or
excision at the polymer linkage releasing the fluorinated alcohol from
the perfluoropolymer. FTOH has been extracted from textiles (SFT,
2006a) and from different fluorinated materials from industrially
applied to consumer products (Dinglasan-Panlilio and Mabury, 2006).
Our samples from 2006 were analyzed for FTOHs that were detected in
neither leachates nor sediment samples. However, a relatively high
distribution coefficient for 8:2 FTOH (Liu and Lee, 2005), estimated log
KDOC of 5.30 ± 0.29, indicates a potential for dissolved organic carbon
(DOC)-facilitated transport, and the DOC levels might thus be high in
many landfills. PFCAs up to PFDcA have been detected in the water
phase, while PFDcA, PFUnA, PFDoA and perfluorotridecanic acid
(PFTrA) have been detected in sludge (Bossi et al., 2008; Higgins et
al., 2005; Schultz et al., 2006).
Aerobic transformation of 8:2 FTOH in activated sludge and mixed
bacteria culture has been demonstrated (Dinglasan et al., 2004; Wang et
al., 2005) and metabolites commonly found are 8:2 FTCA, 8:2 FTUCA and
PFOA. The sediment sample from landfill E, one of the biggest landfills in
Norway with an estimated waste deposit in 2006 of 6,500,000 m3,
had especially high concentrations of long-chained PFCAs and PFOSA.
The high part of these compounds might be due to a combination of
their properties with higher solid–water distribution coefficient (Kd)
(Higgins and Luthy, 2006), and therefore higher potential for precip-
itation in sedimentation treatment steps, and formation from precursors
over long time deposit in the sediments. The recent result by Busch et al.
(2010) showing higher PFC levels in leachates after wet air oxidation
and biological treatment, strengthens this theory. Interestingly, PFBS
that was detected in only a few leachate samples and in low
concentrations (maximal value 20 ng/L) in data presented in our report
were measured in most sediments, and at relatively high concentra-
tions. PFBS has been reported in an average concentration of 37.3
(Woldegiorgis et al., 2006), 51.5 (Kallenborn et al., 2004), 220 ng/L
(Busch et al., 2010) and not detected by others (3M, 2001; Bossi et al.,
2008). Even so, an examination of their potential as sources for the
PFCAs that are readily observed in WWTP, sludge, and landfill leachate,
needs to be explored.
3.2.2. PPCPs
Toxicological studies have provided evidence that the environ-
mental presence of highly bioactive drug residues may produce
 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157 5155

harmful effects to biota even at low concentration (Daughton and
Ternes, 1999; Henschel et al., 1997; Isidoria et al., 2005; Zurita et al.,
2007). Particularly, a cocktail of drugs, endocrine active compounds,
and “classical” pollutants such as phenols, pesticides, halogenated,
and aromatic compounds might constitute increased risks for ecosys-
tems. For instance, the stability of biofilms is inferred by e.g.
carbamazepin a neuroleptic drug frequently applied worldwide
(Lawrence et al., 2005). The pharmaceuticals, paracetamol, phenazone,
and gemfibrozil were not detected in any of the samples in the present
study, while the non-steroidal anti-inflammatory drug (NSAID),
ibuprofen, was detected in all samples from landfill A (Table 4). The
highest ibuprofen concentration of 166,624 ng/L, was measured in
leachate from the inactive part (W-old) of landfill A, decreasing
downstream to 96.9 ng/L at W-inlet. The finding of high ibuprofen
concentrations in the landfills is not surprising, since ibuprofen is among
the top ten non-prescription pharmaceuticals according to sales report
(http://www.legemiddelforbruk.no/) and also among the ten most
commonly prescribed drugs in Norway (Rønning et al., 2008), and
might therefore be explained by previous deposition of wastes
containing unused drugs from both hospitals and households. Ibuprofen
concentrations at μg/L have been reported even in groundwater wells
(Heberer et al., 1998), illustrating the remarkable passage of this acidic
drug (log Kow 2.2) through soil. Due to its polar properties, ibuprofen is
rarely adsorbed, it was neither detected in sediment from leachate
treatment systems (SFT, 2006b), nor in the particle phase of samples
from the present study. In a previous study, it was demonstrated that
sedimentation processes alone will not efficiently eliminate ibuprofen
from wastewater (Carballa et al., 2007). Naproxen, another NSAID, was
measured in the leachate from the W-active of landfill A at a
concentration of 282 ng/L. Compared to ibuprofen, the lower concen-
tration level of naproxen probably reflects a lower deposition volume
and/or a faster degradation with shorter half-life (9–14 days) compared
to ibuprofen (32 days) (Araujo et al., 2009; Tixier et al., 2003).
The neuroleptic drug carbamazepine applied as an anti-epileptic
drug and anti-depressive was measured at trace concentration of 8.6 ng/
L in W-active of landfill A and at W-inlet at 0.8 μg/L. Despite these trace
levels, carbamazepine is one of the most distributed drugs in the
environment (Clara et al., 2004; McClellan and Halden, 2010; Zhang et
al., 2008). Due to its persistence and semi-polar properties, carbama-
zepine can reach groundwater and has been detected in drinking water
(Donn et al., 2008).
In landfill A leachates, the concentrations of both polycyclic musk
compounds AHTN and HHCB are summarized (Table 4) and discussed
together as a marker for the group of musk compounds used in various
household products and cosmetics. The occurrence of polycyclic musk
compounds was comparable to ibuprofen, with the highest concen-
tration in leachates from the W-old of the landfill showing 482,000 ng/
L in the water phase, and with decreasing concentration downstream
of the landfill. Owing to their more hydrophobic properties (HHCB log
Kow 5.9, AHTN log Kow 5.7) (Balk and Ford, 1999)), these polycyclic
musk substances are adsorbed on surfaces of suspended matter and
detected in both the water- and particle phases. The particle-bounded
amount of musk, presented as the sum of AHTN and HHCB, at W-active
and 200 m downstream (W-inlet) of landfill A were 9.6 and 17.9 ng/L,
respectively. The corresponding water phase contribution was 6.5 and
3 ng/L, respectively, indicating transportion via both water- and
particle phases through the sandy aquifer of the landfill. The
particle-bound musk contribution in leachates from landfill B, taken
at the discharge of the WWTP drainage system, was 27 ng/L. The
relatively lipophilic HHCB has been observed in the range of 43–
63 mg/kg dw sewage sludge in previous studies focusing on the
environmental fate of musk compounds (Carballa et al., 2007)
3.3. Non-emerging compounds identified in the full scan analysis
Generally, phenols and alkylated benzenes were the dominating
compounds detected in the leachates (approximately 25–40% of the
total detected compounds). The use of phenolic compounds is
widespread in industrial products, such as plastic softeners, lacquers,
paints and as antioxidants in fuels and oil. Furthermore, non-
halogenated short-alkyl chain phenols and carboxylated phenols are
also typical breakdown products of (poly)aromatic substances
(Cajthaml et al., 2006) and of natural polymers like polyphenols and
lignin. The alkylated phenols, di-tert-butylphenols, nonylphenol (NP)
and bisphenol-A (BPA), as well as C4-benzenes were detected in all
leachate samples (Table 3). Due to a natural potential of many
microbes to degrade and metabolize phenols, this group of pollutants
disappear fairly rapidly from the environment. Thus, risks related with
the presence of various phenolic compounds can be reduced by
stimulating microbial activity in the leachate environment.
The majority of compounds previously identified in municipal
landfill leachate, such as terpenoids, aromatic acids, phenols, aliphatic
acids, aliphatic alcohols, esters, ethers, are derived from decomposing
vegetation and degradation products of natural materials (Reinhard et
al., 1984; Schwarzbauer et al., 2002). Terpenoids commonly found in
leachates are camphor, α-terpineol, fenchone, limonene, and pinene
compounds (Schwarzbauer et al., 2002; Slack et al., 2005; Welander,
1997). In the present study and based on semi-quantitative evaluation —
camphor, limonene, and pinene were detected in the μg/L range in most
leachates. These compounds are widely used odorants, technically
manufactured or released during plant degradation. Camphor for
instance, is also used as plasticizer in the manufacture of cellulose
nitrate film. Many of these compounds tend to decompose in the
leachate during migration (Leenheer et al., 2003; Reinhard et al., 1984;

Table 4
Pharmaceutical and personal care products (PPCPs) investigated in water- and particle phases at landfill A and in particle phase at landfill B. Data is given as concentration in ng/L for
water- and particle phase.

Landfill A Landfill B Literature data

Water phase Particle phase Particle phase

Discharge
W-old W-active W-50 W-100 Discharge W-active W-inlet

Ibuprofen 166,624 1067 1884 6888 69.9 b0.1 b 0.1 b 0.1 610, 200 (Schwarzbauer et al., 2002; SFT, 2006b;
Heberer et al., 1998)
Paracetamol b2 b2 b2 b2 96.9 b2 b2 b2
Phenazon b3 b3 b3 b3 b3 b3 b3 b3 b 10–1250 (Heberer et al., 1998)
Gemfibrozil b 0.1 b0.1 b0.1 b 0.1 b 0.1 b0.1 b 0.1 b 0.1 190–340 (Heberer, 2002)
Naproxen b 0.3 282.0 b0.3 b 0.3 b 0.3 b0.3 b 0.3 b 0.3 520 (Daughton and Ternes, 1999)
Carbamacepin b2 8.6 b2 b2 0.8 b2 b2 b2 1000–6300 (Kosjek et al., 2009)
AHTN + HHCB 481,906 6.5 5.3 44.2 2.9 9.6 17.9 26.8 4300–63,000 μg/kg d.w. sludge
(Kupper et al., 2004; Mogensen et al., 2004)

b LOQ: below limit of quantification, LOQ for HHCB and AHTN is 2 ng/L.
5156 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157
Schwarzbauer et al., 2002). Compounds identified in all three wells
downstream of landfill A are fatty acids, fatty acid esters, and benzoic
acids (Table 3), which are typical metabolites and products of microbial
degradation of carbohydrates, PAHs and aromatic pollutants (Cajthaml
et al., 2006). Furthermore, fatty acids, fatty acid esters, and benzoic acids
can also arise from biological material.
3.4. Conclusions and environmental significance
Emerging compounds identified in our untreated leachate samples
at nanogram (ng) or microgram (μg) per liter levels were chlorinated
alkylphosphates including the possible carcinogenic flame retardant
(TCPP), the neurotoxin plasticizer (NBBS), the insect repellent (DEET),
PFCs, pharmaceuticals and personal care products such as the NSAIDs
(ibuprofen and naproxen) and polycyclic musk compounds. In addition,
legacy contaminants such as PAHs and phthalates were detected. The
societal concerns of the emerging compounds, namely — PFCs,
organophoastes, DEET and NBBS is related to both their chemical
properties and possible environmental and human health effects. Many
emerging compounds are identified at higher levels in the water phase
than the particle phase and since they also seem to be rather persistent,
they might be pose significant removal challenge in treatment
processes. Commonly applied treatment methods for landfill leachates
are based on short-term biological degradation, aeration and sedimen-
tation processes. For effective removal of these types of emerging
compounds, it might be necessary to apply other treatment processes
such as membrane technologies or reverse osmosis. Given that the
composition of pollutant mixtures varies qualitatively and quantita-
tively, a combined treatment protocol that includes different processes
should be preferred.
The high concentration of PFCs measured in the leachate water
phase from landfills in the present study is of particular concern.
Furthermore, several PFCs such as long-chained PFCAs, not identified in
either water or particle phases in leachates may be present in relatively
high concentrations in sediments taken from treatment systems from
landfill leachates, indicating their formation during transformation of
perfluorinated precursors that are yet to be identified. For example,
polyfluoroalkyl phosphoric acids (PAPs) which are used in human food
contact paper products was recently suggested to be a precursor for
PFCAs (D'eon et al., 2009b). Landfill leachates have been suggested to be
a less important source of PFCs (Bossi et al., 2008; Busch et al., 2010).
However, the high variations of PFC concentrations reported in the
present study and elsewhere suggest a high variation in loading and
contribution from landfills and in certain locations might produce
higher environmental and health concerns. Additional knowledge about
the environmental fate and toxicology of emerging compounds is
necessary in order to address the need for improved treatment
technologies for sustainable and efficient removal of these compounds.
Overall, the present have shown that municipal landfills play an integral
role as possible sources for new and emerging perfluorinated
substances, pharmaceuticals, musk compounds, in addition to poten-
tially other compounds not measured. Furthermore, the use of non-
target full scan analysis proves to be a useful tool for early detection and
search for sources for groups of compounds in the environment.
Acknowledgments
We are grateful to Hans Ragnar Norli at Bioforsk and Steffi
Schrader at the Helmholtz Centre for Environmental Research,
Department of Analytical Chemistry for their support in preparation
and analysis of the leachate samples. The PFC analysis was performed
at Norwegian Institute of Air Research, The Polar Environmental
Centre. We thank the Norwegian Research Council for financial
support (project numbers 151335/720 and 162865 to TE and project
number 178611/S40 to AA).
References
OECD. Tris(1-chloro-phosphate)phosphate. UNEP Publication.
3M. Environmental monitoring — multi-city-study water, sludge, sediment, POTW
effluent and landfill leachate samples. 3M Environmental Laboratory; 2001.
Ahrens L, Plassmann M, Xie Z, Ebinghaus R. Determination of polyfluoroalkyl
compounds in water and suspended particulate matter in the river Elbe and
North Sea, Germany. Front Environ Sci Eng China 2009;3:152–70.
Andreozzi R, Marotta R, Pinto G, Pollio A. Carbamazepine in water: persistence in the
environment, ozonation treatment and preliminary assessment on algal toxicity.
Water Res 2002;36:2869–77.
Araujo L, Villa N, Camargo N, Bustos M, García T, de Jesus Prieto A. Persistence of
gemfibrozil, naproxen and mefenamic acid in natural waters. Environ Chem Lett
2009, doi:10.1007/s10311-009-0239-5.
Balk F, Ford RA. Environmental risk assessment for the polycyclic musks AHTN and
HHCB in the EU. I. Fate and exposure assessment. Toxicol Lett 1999;111:57–79.
Barnes KK, Christenson SC, Kolpin DW, Focazio MJ, Furlong ET, Zaugg SD, et al.
Pharmaceuticals and other organic waste water contaminants within a leachate
plume downgradient of a municipal landfill. Ground Water Monit Rem 2004;24:
119–26.
Bauer MJ, Herrmann R. Dissolved organic carbon as the main carrier of phthalic acid
esters in municipal landfill leachates. Waste Manage Res 1998;16:446–54.
Bossi R, Strand J, Sortkjær O, Larsen MM. Perfluoralkyl compounds in Danish wastewater
treatment plants and aquatic environments. Environ Int 2008;34:443–50.
Braun P, Möder M, Schrader S, Popp P, Kuschk P, Engewald W. Trace analysis of
technical nonylphenols, bisphenol A and 17a-ethinylestradiol in wastewater using
gas chromatography-mass spectrometry. J Chromatogr A 2003;988:41–51.
Busch J, Ahrens L, Sturm R, Ebinghaus R. Polyfluoroalkyl compounds in landfill
leachates. Environ Pollut 2010;158:1467–71.
Cajthaml T, Erbanova P, Sasek V, Moeder M. Breakdown products on metabolic pathway
of degradation of benz[a]anthracene by a ligninolytic fungus. Chemosphere
2006;64:560–4.
Carballa M, Omil F, Lema JM. Calculation methods to perform mass balances of
micropollutants in sewage treatment plants. Application to pharmaceutical and
personal care products (PPCPs). Environ Sci Technol 2007;41:884–90.
Clara M, Strenn B, Kreuzinger N. Carbamazepine as a possible, anthropogenic marker in
the aquatic environment: investigations on the behaviour of carbamazepine in
wastewater treatment and during groundwater infiltration. Water Res 2004:
947–54.
Corbel V, Stankiewicz M, Pennetier1 C, Fournier C, Stojan6 J, Girard E, et al. Evidence for
inhibition of cholinesterases in insect and mammalian nervous systems by the
insect repellent DEET. BMC Biol 2009;7, doi:10.1186/1741-7007-7-47.
Daughton CG, Ternes TA. Pharmaceuticals and personal care products in the
environment: agents of subtle change? Environ Health Perspect 1999;107:907–37.
D'eon JC, Crozier PW, Furdui VI, Reiner EJ, Libelo EL, Mabury SA. Observation of a
commercial fluorinated material, the polyfluoroalkyl phosphoric acid diesters, in
human sera, wastewater treatment plant sludge, and paper fibers. Environ Sci
Technol 2009a;43:4589–94.
D'eon JC, Crozier PW, Furdui VI, Reiner EJ, Libelo EL, Mabury SA. Perfluorinated
phosphonic acids in Canadian surface waters and wastewater treatment plant
effluent: discovery of a new class of perfluorinated acids. Environ Toxicol Chem
2009b;28:2101–7.
Dinglasan MJA, Ye Y, Edwards EA, Mabury SA. Fluorotelomer alcohol biodegradation
yields poly- and perfluorinated acids. Environ Sci Technol 2004;38:2857–64.
Dinglasan-Panlilio MJA, Mabury SA. Significant residual fluorinated alcohols present in
various fluorinated materials. Environ Sci Technol 2006;40:1447–53.
Donn J, Mendoza M, Pritchard J. Drugs found in drinking water. Associated Press; 2008.
http://www.usatoday.com/news/nation/2008-03-10-drugs-tap-water_N.htm.
Fjeld E, Schlabach M, Berg JA, Green N, Eggen T, Snilsberg P, et al. Mapping of selected
emerging organic pollutants. SFT report 2004. TA-2096/2005; 2005.
Heberer T. Occurrence, fate, and removal of pharmaceutical residues in the aquatic
environment: a review of recent research data. Toxicol Letters 2002;131:5-17.
Heberer T, Schmidt-Bäumler R, Stan H-J. Occurrence and distribution of organic
contaminants in the aquatic system in Berlin. Part I. Drug residues and other polar
contaminants in Berlin surface and groundwater. Acta Hydrochim Hydrobiol
1998;26:272–8.
Hekster FM, Laane RWPM, DeVoogt P. Environmental and toxicity effects of
perfluoroalkylated substances. Rev Environ Cont Toxicol 2003;179:99-121.
Henschel K-P, Wenzel A, Diedrich M, Fliedner A. Environ. hazard assessment of
pharmaceuticals. Regul Toxicol Pharmacol 1997;25:220–5.
Higgins CP, Luthy RG. Sorption of perfluorinated surfactants on sediments. Environ Sci
Technol 2006;40:7251–6.
Higgins CP, Field JA, Criddle CS, Luthy RG. Quantitative determination of perfluorochem-
icals in sediments and domestic sludge. Environ Sci Technol 2005;39:3946–56.
http://www.legemiddelforbruk.no/.
Holm JV, Rügge K, Bjerg PL, Christensen TH. Occurrence and distribution of
pharmaceutical organic compounds in the groundwater downgradient of a landfill
(Grindsted, Denmark). Environ Sci Technol 1995;29:1415–20.
Isidoria MT, Lavorgnaa M, Nardellia A, Parrellaa A, Previterab L, Rubinob M. Ecotoxicity
of naproxen and its phototransformation products. Sci Total Environ 2005;348:
93-101.
Kallenborn R, Berger U, Järnberg U. Perfluorinated alkylated substances (PFAS) in the
Nordic environment. Tema Nord, 2004. Nordic Council of Ministers92-893-1051-0;
2004. p. 552.
Kannan K, Corsolini S, Falandysz J, Oehme G, Focardi S, Giesy JP. Perfluorooctanesulfo-
nate and related fluorinated hydrocarbons in marine mammals, fishes, and
 T. Eggen et al. / Science of the Total Environment 408 (2010) 5147–5157
birds from coasts of the Baltic and the Mediterranean Seas. Environ Sci Technol
2002;36:3210–6.
Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, et al.
Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S.
streams, 1999–2000: a national reconnaissance. Environ Sci Technol 2002;36:
1202–11.
Kosjek T, Andersen HR, Kompare B, Ledin A, Heath E. Fate of Carbamazepine during
Water Treatment. Environ Sci Technol 2009;43:6256–61.
Kuhn EP, Suflita JM. Anaerobic biodegradation of nitrogen-substituted and
sulfonated benzene aquifer contaminants. Hazard Waste Hazard Mater 1989;6:
121–33.
Kupper T, Berset JD, Etter-Holzer R, Furrer R, Tarradellas. Concentrations and specific
loads of polycyclic musks in sewage sludge originating from a monitoring network
in Switzerland. Chemosphere 2004;54:1111–20.
Lawrence JR, Swerhone GDW, Wassenaar LI, Neu TR. Effects of selected pharmaceuticals
on riverine biofilm communities. Can J Microbiol 2005;51:655–69.
Leahy JGC, Colwell RR. Microbial degradation of hydrocarbons in the environment.
Microbiol Rev 1990;54:305–15.
Leenheer JA, Nanny MA, McIntyre C. Terpenoids as major precursors of dissolved
organic matter in landfill leachates, surface water, and groundwater. Environ Sci
Technol 2003;37:2323–31.
Liu J, Lee LS. Solubility and sorption by soils of 8:2 Fluorotelomer alcohol in water and
cosolvent systems. Environ Sci Technol 2005;39:7535–40.
Martin J, Smithwich MM, Braune BM, Hoekstra PF, Muir DCG, Mabury SA. Identification
of long-chain perfluorinated acids in biota from the Canadian Arctic. Environ Sci
Technol 2004;38:373–80.
McClellan K, Halden RU. Pharmaceuticals and personal care products in archived U.S.
biosolids from the 2001 EPA national sewage sludge survey. Water Res 2010;44:
658–68.
Möder M, Braun P, Lange F, Schrader S, Lorenz W. Highly selective and sensitive
determination of endocrine disrupting compounds and pharmaceutical residues
using solid phase extraction, derivatization and gas chromatography — negative
chemical ionization mass spectrometry. CLEAN 2007;35:441–51.
Mogensen BB, Pritzl G, Rastogi S, Glesne O, Hedlund B, Hirvi J-P, et al. Musk compounds
in the Nordic environment. TemaNord 2004;2004:503.
Öman C, Hynning P-Å. Identification of organic compounds in municipal landfill
leachates. Environ Pollut 1993;80:265–71.
Paxéus N. Organic compounds in municipal landfill leachates. Water Sci Technol
2000;42:323–33.
Prince RC. Petroleum spill bioremediation in marine environments. Crit Rev Microbiol
1993;19:217–42.
Reinhard M, Goodman NL, Barker JF. Occurrence and distribution of organic chemicals
in two landfill leachate plumes. Environ Sci Technol 1984;18:953–61.
Rimkus GG. Polycyclic musk fragrances in the aquatic environment. Toxicol Lett
1999;111:37–56.
Rivera-Cancel G, Bocioaga D, Hay AG. Bacterial Degradation of N, N-Diethyl-m-
Toluamide (DEET): cloning and heterologous expression of DEET hydrolase. Appl
Environ Microbiol 2007;73:3105–8.
5157
Rønning M, Berg CL, Furu K, Litleskare I, Sakshaug S, Strøm H. The Norwegian
prescription database 2004–2007. In: Rønning M, editor. Oslo: The Norwegian
Institute of Public Health; 2008.
Salvito D. Synthetic musk compounds and effects on human health? Environ Health
Perspect 2005;113:A802–3.
Schultz MM, Higgins CP, Huset CA, Luthy G, Barofsky DF, Field JA. Fluorochemicals mass flows
in a municipal wastewater treatment facility. Environ Sci Technol 2006;40:7350–7.
Schwarzbauer J, Heim S, Brinker S, Littke R. Occurrence and alteration of organic
contaminants in seepage and leakage water from a waste deposit landfill. Water
Res 2002;36:2275–87.
SFT. Mapping of perfluroalkylated substances (PFAS) in selected textils Norwegian
Pollution Control Authority report: TA-2173/2006; 2006a.
SFT. Screening of selected pharmaceuticals and cosmetic compounds Norwegian
Pollutant Control Authority TA-2156/2006 (In Norwegian, extended abstract in
English); 2006b.
Sinclair E, Kannan K. Mass loading and fate of perfluoroalkyl surfactants in wastewater
treatment plants. Environ Sci Technol 2006;40:1408–14.
Slack RJ, Gronow JR, Voulvoulis N. Household hazardous waste in municipal landfills:
contaminants in leachate. Sci Total Environ 2005;337:119–37.
Strong MJ, Garruto RM, Wolff AV, Chou SM, Fox SD, Yanagihara R. N-butyl
benzenesulfonamide — a neurotoxic plasticizer inducing a spastic myelopathy in
rabbits. Acta Neuropathol 1991;81:235–41.
Ternes TA. Occurrence of drugs in German sewage treatment plants and rivers. Water
Res 1998;32:3245–60.
Ternes TA. Pharmaceuticals and metabolites as contaminants of the aquatic
environment. Scientific and Regulatory Issues. In: Daughton CG, Jones-Lepp T,
editors. American Chemical Society, Symposium Series, 791. ; 2001. p. 39–54.
Washington DC.
Tixier C, Singer HP, Oellers S, Müller SR. Occurrence and fate of carbamazepine, clofibric
acid, diclofenac, ibuprofen, ketoprofen, and naproxen in surface waters. Environ Sci
Technol 2003;37:1061–8.
Wang N, S.B., Buck RC, Folsom PW, Sulecki LM, Capka V, et al. Fluorotelomer alcohol
biodegradation — direct evidence that perfluorinated carbon chains breakdown.
Environ Sci Technol 2005;39:7516–28.
Welander U. Identification by Gas Chromatography of organic constituents in leachates
from sanitary landfills. Resour Environ Biotechnol 1997;1:283–96.
Westerhof P, Yoon Y, Snyder S, Wert E. Fate of endocrine-disruptor, pharmaceutical,
and personal care product chemicals during simulated drinking water treatment
processes. Environ Sci Technol 2005;39:6649–63.
Woldegiorgis A, Andersson J, Remberger M, Kaj L, Ekheden LB, Brorström-Lundén E,
et al. Results from the Swedish National Screening Programme 2005. Subreport 3:
perfluorinated alkylated substances (PFAS). IVL Swedish Environmental Research
Institute. Report B1698; 2006.
Zhang Y, Geißen S-U, Gal C. Carbamazepine and diclofenac: removal in wastewater
treatment plants and occurrence in water bodies. Rev Chemosphere 2008;73:1151–61.
Zurita JL, Repetto G, Jos A, Salguero M, Lopez-Artiguez M, Camean AM. Toxicological
effects of the lipid regulator gemfibrozil in four aquatic systems. Aquat Toxicol
2007;81:106–15.