Chemosphere 122 (2015) 168–175
Contents lists available at ScienceDirect
Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere
Dioxins and dioxin-like compounds in composts and digestates from
European countries as determined by the in vitro bioassay and chemical
analysis
Martin Beníšek a, Petr Kukučka a, Giulio Mariani b, Gert Suurkuusk b, Bernd M. Gawlik b, Giovanni Locoro b,
John P. Giesy c,d,e,f, Luděk Bláha a,⇑
a
Masaryk University, Faculty of Science, RECETOX, Brno, Czech Republic
European Commission, DG Joint Research Centre (JRC), Institute for Environment and Sustainability, Unit H.01-Water Resources Unit, Ispra, Italy
c
Department of Veterinary Biomedical Sciences and Toxicology Centre, University of Saskatchewan, SK, Canada
d
Department of Biology & Chemistry and State Key Laboratory in Marine Pollution, City University of Hong Kong, Kowloon, Hong Kong Special Administrative Region
e
School of Biological Sciences, University of Hong Kong, Hong Kong Special Administrative Region
f
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, People’s Republic of China
b
h i g h l i g h t s
Pan-European study of dioxins and dioxin-like compounds in composts and digestates.
PCDD/Fs, PCBs, OCPs, PAHs and dioxin effects compared in various types of samples.
Compliance with conservative limits confirmed for most of the samples.
High added value of the biodetection tools and effect-based monitoring demonstrated.
a r t i c l e
i n f o
Article history:
Received 18 July 2014
Received in revised form 11 November 2014
Accepted 15 November 2014
Available online 15 December 2014
Handling Editor: Gang Yu
Keywords:
Biodetection tools
Effect-based monitoring
Dioxin
PAHs
Compost
Digestate
⇑ Corresponding author.
http://dx.doi.org/10.1016/j.chemosphere.2014.11.039
0045-6535/Ó 2014 Elsevier Ltd. All rights reserved.
a b s t r a c t
Aerobic composting and anaerobic digestion plays an important role in reduction of organic waste by
transforming the waste into humus, which is an excellent soil conditioner. However, applications of chemical-contaminated composts on soils may have unwanted consequences such as accumulation of persistent
compounds and their transfer into food chains. The present study investigated burden of composts and digestates collected in 16 European countries (88 samples) by the compounds causing dioxin-like effects as
determined by use of an in vitro transactivation assay to quantify total concentrations of aryl hydrocarbon
receptor-(AhR) mediated potency. Measured concentrations of 2,3,7,8-Tetrachlorodibeno-p-dioxin
(2,3,7,8-TCDD) equivalents (TEQbio) were compared to concentrations of polycyclic aromatic hydrocarbons
(PAHs) and selected chlorinated compounds, including polychlorinated dibenzo-p-dioxins/furans (PCDD/
Fs), co-planar polychlorinated biphenyls (PCBs), indicator PCB congeners and organochlorine pesticides
(OCPs). Median concentrations of TEQbio (dioxin-like compounds) determined by the in vitro assay in crude
extracts of various types of composts ranged from 0.05 to 1.2 with a maximum 8.22 lg (TEQbio) kg 1 dry
mass. Potencies were mostly associated with less persistent compounds such as PAHs because treatment
with sulfuric acid removed bioactivity from most samples. The pan-European investigation of contamination by organic contaminants showed generally good quality of the composts, the majority of which were
in compliance with conservative limits applied in some countries. Results demonstrate performance and
added value of rapid, inexpensive, effect-based monitoring, and points out the need to derive corresponding effect-based trigger values for the risk assessment of complex contaminated matrices such as
composts.
Ó 2014 Elsevier Ltd. All rights reserved.
M. Beníšek et al. / Chemosphere 122 (2015) 168–175
1. Introduction
Composting (aerobic process) and digestion (anaerobic process)
can be useful for reduction of various wastes, because these processes can transform organic waste to humus, which is an excellent
soil conditioner (Grossi et al., 1998). On the other hand, the presence of or formation of persistent toxicants in composts or digestates is an issue that might limit their widespread use. Use of
compost and digestate as amendments to improve fertility increase
organic matter, reduce erosion, and improve physical chemical
properties of soils such as retention of water (Semple, 2001;
Pedra et al., 2007). There are several requirements placed on quality
of compost that need to be met to protect the environment from
adverse effects of both inorganic and organic contaminants. The
most important parameters include minimum content of metals
and organic chemicals at toxic concentrations and the absence of
pathogens that pose risks to health of humans (Lasaridi et al.,
2006). Composts and digestates can be contaminated by various
chemicals that can cause adverse effects on humans and wildlife.
While heavy metals in composts are relatively well studied and
controlled, there is still limited knowledge about the content, fate
and effects of organic pollutants. The focus of this study was
persistent organic pollutants (POPs), including organochlorine
insecticides (OCs), constituents of personal care products, industrial
chemicals, such as polychlorinated biphenyls (PCBs), polycyclic
aromatic hydrocarbons (PAHs), and polychlorinateddibenzop-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF)
(Brändli et al., 2007a,b; Grossi et al., 1998; Hseu, 2004). Some
non-persistent organic pollutants, such as lesser molecular mass
PAHs, can be degraded during composting (Brändli et al., 2007b),
but other contaminants such as PCBs or PCDDs/Fs could accumulate
in soil when contaminated compost or digestate is applied repeatedly (Umlauf et al., 2011). In several European countries some limit
values for the content of organic pollutants such as PCDDs/Fs, PCBs,
PAHs and others have been established (Saveyn and Eder, 2014;
WRAP, 2002).
Various toxic effects have been associated with the above mentioned organic pollutants. Probably the most important and most
widely studied is activation of the arylhydrocarbon receptor
(AhR) which results in dioxin-like toxicity (Sorg, 2013). Toxic
potential of dioxin-active compounds is often calculated from the
results of chemical analyses using the Toxic Equivalency, TEQ,
approach (I-TEQ or WHO-TEQ) (Lee et al., 2013). TEQs, to calculate
equivalents of 2,3,7,8-tetrachlorodibenzo-p-dioxin, (TCDD) (usually expressed in ng of TCDD per kg material) are calculated as
the sum of the product of concentrations of individual AhR-active
compounds multiplied by their corresponding toxic equivalency
factors (TEFs), or relative response factors (Lee et al., 2013;
Machala et al., 2001). In addition, TEQbio can be estimated by use
of bioanalytical tools such as ethoxyresorufin O-deethylase (EROD)
assay (Joung et al., 2007) or transactivation, reporter gene bioassays, such as H4IIE-luc cells (Giesy et al., 2002), DR-CALUX (Murk
et al., 1996) and others where expression of the reporter gene,
luciferase, is up-regulated by exposure to agonists of the AhR.
Both chemical and biological methods used for the analyses of
dioxin-active compounds have their specific advantages and disadvantages. Chemical analysis allows assessment of only a limited
number of compounds such as the 17 US EPA PCDDs/Fs or 16 US
EPA PAHs, while bioanalytical methods measure the integrated
potency of all AhR-active compounds present in the sample including also e.g. brominated derivatives (Samara et al., 2009) or various
PAH metabolites and analogs (Sovadinova et al., 2006). Chemical
analysis can also be costly, especially when considering analyses
of PCDD/Fs and co-planar PCBs (Joung et al., 2007). The concept
of chemical TEQs is based on additive effects of toxic compounds
169
but these compounds present in complex samples might elicit
infra- or supra-additive interactions (Suzuki et al., 2006), which
can be detected by the use of biodetection tools. Bioanalytical
detection systems can also be more sensitive because they are
responding to the complex of chemicals in aggregate instead of
each chemical individually. Alternatively, limitations of bioanalytical tools include greater variability which is natural to biological
testing systems, a lesser degree of standardization and generally
lesser acceptance by regulatory authorities. Nevertheless, the
effect-based monitoring is becoming widely applied (Escher
et al., 2013; Hecker and Giesy, 2011) and certain biodetection tools
have already been standardized and suggested for practical use,
including the assessment of endocrine disruptive (estrogenic)
(ISO, 2014) or dioxin-like compounds (Hecker and Giesy, 2011).
Concentrations of persistent organic pollutants and PAHs in
composts determined by chemical analyses have been reported
previously (Grossi et al., 1998; Brändli et al., 2007a,b) and some
studies also investigated the dioxin-like activity using the
biodetection tools such as H4IIE-luc cells (Takigami et al., 2010;
Suzuki et al., 2006). However, detailed comparisons of the chemical- and effect-based monitoring of AhR active compounds using
the broader set of compost samples are few. In previous studies
some PAHs such as benzo[k]fluoranthene, dibenz[a,h]anthracene
or benzo[a]pyrene detected in composts (Brändli et al., 2007a)
were shown to be potent inducers of AhR in vitro (Machala et al.,
2001). Also some other PAHs, which may have lesser dioxin-like
potentials (IEF – Induction Equivalency Factor) but great abundance in composts (such as fluoranthene and others) could significantly contribute to the dioxin-like effects of the whole sample
(Lee et al., 2013). Available data on concentrations of persistent
organic pollutants indicate that composts contain congeners with
lesser TEFs or IEFs such as octachlorodibenzo-p-dioxin or
heptachlorodibenzo-p-dioxin (OCDD or HpCDD) (Takigami et al.,
2010; Muñoz et al., 2013). In addition to PCDDs/Fs and dioxin-like
PCBs, other chlorinated compounds could be found in composts
including organochlorinated pesticides (OCPs) such as dichlorodiphenyltrichloroethane (DDT), hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), pentachlorobenzene (PeCB) and others
(Brändli et al., 2004). Although toxicity of these compounds is
not primarily mediated via the AhR, some have been shown to
act as weak AhR agonists and could also contribute to the effect
of the whole mixture (Mrema et al., 2013). To our knowledge, concentrations of other potential AhR-acting dioxin-like compounds
(such as polybrominated diphenyl ethers, PBDEs) have only rarely
been investigated in compost or digestates. In summary, the available data indicate that PAHs may be the dominant compounds contributing to the dioxin-like effects of the complex compost samples
but the role of different AhR-active compounds has not been studied in detail.
The main objective of the present study was to investigate concentrations of a range of compounds causing dioxin-like toxicity in
composts and digestates collected throughout 16 countries in
Europe. The present study compared the concentrations of PAHs
and diverse chlorinated compounds (indicator PCBs, OCPs, PCDD/
Fs and co-planar PCBs) with dioxin-like effects observed in vitro.
2. Materials and methods
2.1. Design of the study
The present study investigated various categories of composts
such as organic waste from households, green compost from gardens and parks, sewage sludge compost and also some composts
and digestates after Mechanical Biological Treatment. Screening
170
M. Beníšek et al. / Chemosphere 122 (2015) 168–175
of crude organic extracts of 88 samples of composts was performed
by use of the H4IIE-luc bioassay while PAHs were also quantified.
Based on results of the screening, seventeen samples were selected
for detailed chemical analysis of PCDDs/Fs, PCBs and other organochlorine compounds. In addition, dioxin-like activity was tested in
this subset of samples also after the treatment of the sulfuric acid
(H2SO4) which is known to remove labile compounds (such as
PAHs) retaining only highly persistent organochlorine compounds.
2.2. Compost samples
Composts and digestates were collected and provided by the
owners of various compost plants all over the Europe. The sampling according to EN 12579 was recommended but with respect
to the pan-European character of the study, complete standardization was not possible and each plant was allowed to collect the
samples using their own protocol. Overall, 96 composts or digestates were collected from which 88 samples (from 16 European
countries) were selected, divided into categories, and analyzed.
The respective categories were:
(A) Compost produced from separately collected organic waste
from households and similar commercial institutions, including
garden and park waste; (B) compost produced from garden and
park waste only (green compost); (C) sewage sludge compost
produced from good quality sewage sludge and other separately
collected organic waste (e.g. garden and park waste, straw, etc.);
(D) Municipal Solid Waste compost generated by Mechanical Biological Treatment (MBT) aimed at producing compost (derived
from non-hazardous household waste and similar commercial
waste where no separate collection of household waste is in place);
(E) biowaste digestates from source separated biowaste from
households and similar commercial institutions (not investigated
in the present study for technical reasons); (F) digestates from
manure and source separated biowastes from households and similar commercial institutions; (G) digestates from manure and
energy crops; (H) digestate derived from Mechanical Biological
Treatment of Municipal Solid Waste, aimed at producing digestate
for use in agriculture (derived from nonhazardous household
waste and similar commercial waste); (I) other, minor categories.
These include bark compost or Municipal Solid Waste compost like
output generated by Mechanical Biological Treatment aimed at
stabilizing a rest fraction sent to landfill.
2.3. Processing of samples for biological analyses
Lyophilized samples (2 g, dry mass; dm) were extracted (automated warm Soxhlet extractor, BüchiB-811, Switzerland) by
dichloromethane (DCM) (150 mL, 2 h). Extracts were evaporated
to approximately 5 mL and transferred to vials. Samples were concentrated by nitrogen stream to the last drop and then dissolved in
methanol (0.5 mL) and stored frozen until testing. For 17 selected
samples, aliquots (200 lL) were treated with sulfuric acid silica
column to remove less persistent pollutants like PAHs. Persistent
organic compounds were then eluted from the column by a mixture of dichloromethane/hexane (40 mL), concentrated by nitrogen
stream. One aliquot of the sample was used for analyses of persistent compounds and the second aliquot was evaporated, dissolved
in methanol and tested for their dioxin-like effects in vitro using
the H4IIE-luc bioassay.
2.4. Quantification of PAHs
All native and labeled mixture standards of PAHs were
purchased from Chiron AS (Norway). Custom PAH Neat Standard
Mixture (Product No. S-4582-25-IO, batch 9184) containing: Phenanthrene, Anthracene, Fluoranthene, Pyrene, Benzo(a)anthracene,
Chrysene, Benzo(b)fluoranthene, Benzo(k)fluoranthene, Benzo(e)pyrene,
Benzo(a)pyrene,
Perilene,
Indeno(1,2,3-cd)pyrene,
Dibenzo(a,h)anthracene, Benzo(g,h,i)perilene, Dibenzo(a,l)pyrene,
Dibenzo(a,h)pyrene, Dibenzo(a,i)pyrene, Dibenzo(a,e)pyrene and
Coronene. Custom PAH Surrogate Standard Mixture (Product No.
S-4582-50-IO, batch 92010) containing: Phenanthrene-d10,
Anthracene-d10, Fluoranthene-d10, Pyrene-d10, Chrysene-d12,
Benzo(b)fluoranthene-d12, Benzo(e)pyrene-d12, Benzo(a)pyrened12, Perilene-d12, Indeno(1,2,3-cd)pyrene-d12, Dibenzo(a,h)
anthracene-d14, Benzo(g,h,i)perilene-12, Dibenzo(a,i)pyrene-d14,
and Coronene-d12. Custom PAH Syringe Standard Mixture (Product No. S-4581-50-IO, batch 9171) containing: p-Terphenyl-d14,
Benzo(a)anthracene-d12, Benzo(k)fluoranthene-d12. All solvents
(Acetone, n-hexane) were dioxin grade and purchased by Riedelde Haen (Germany).
Lyophilized samples (0.1 g) were spiked with 25 ng of Surrogate
Standard Mixture and extracted twice for 30 min. by ultrasonic
bath with 0.5 mL of a mixture of n-hexane/acetone (80:20, %V/V).
After 25 ng of Syringe Standard Mixture spike the extracts with
added samples were submitted to gas chromatography–mass
spectrometry (GC–MS) analysis. PAHs were analyzed on a high resolution gas chromatography (HRGC) (Agilent 6890N) coupled with
a Mass Selective Detector (Agilent 5973N). For all analytes the
molecular ions were recorded for both native and labeled congeners. Quantified isomers were identified by comparison of retention
times of the corresponding standard. Quantification was performed by isotopic dilution. PAHs were separated on a BPX-50
60 m long with 0.25 mm i.d. (inner diameter) and 0.25 lm films
(SGE, Victoria, Australia). Gas chromatographic conditions were:
PTV injector from 100 to 300 °C at 12 °C s 1, constant flow at
1.0 mL min 1 of He, GC–MS interface at 280 °C. The GC program
rate was: 100 °C with a 3 min hold, then 15 °C min 1 to 220 °C
for 0 min, then 2 °C min 1 to 300 °C for 20 min finally 3 °C min 1
to 340 °C and a final hold of 30 min. The selectivity, linearity,
detection and quantification limits, trueness, repeatability, recovery, and stability of the extracts were determined and the uncertainty estimated. Detailed recoveries and limits of quantifications
for measured PAHs are reported in Supplementary materials
Table S1-part F. The detailed method description was reported by
Tavazzi et al. (2013)
2.5. Analyses of indicator PCBs, OCPs, PCDDs/Fs and dl-PCBs
All standards (PCDDs/Fs, dl-PCBs) were purchased from Wellington Laboratories (Canada) or LGC Europe (PCBs and OCPs).
For indicator PCBs and for organochlorine pesticides, instrumental
analysis used GC Agilent 68890N-: Micromass Qauttro Micro GC
(tandem quadrupole system), splitless injections, columns:
60 m 0.25 mm 0.25 lm DB5-MS (J&W, Agilent, USA). Helium
was used as a carrier gas at constant flow 1.5 mL min 1. quantification of PCDD/Fs and coplanar (dioxin-like, dl) PCBs, aliquots of
extracts prepared in dichloromethane were spiked with internal
standards of 13C PCDDs/Fs (according to EN-1948) and 13C dl-PCBs
(77, 81, 126, 169, 105, 114, 118, 123, 156, 157, 167 and 189). The
concentrated extracts were cleaned-up on a sulfuric acid-modified
(44% w/w) silica column, eluted with 40 mL DCM/n-hexane mixture (1:1). Fractionation was achieved in a micro column (6 mm
i.d.) containing from the bottom to top: 50 mg silica, 70 mg charcoal (Darco G60, Sigma–Aldrich)/silica (1:40) and 50 mg of silica.
The column was pre-washed with 5 mL of toluene, followed by
5 mL of DCM/cyclohexane mixture (30%), then the sample was
applied and eluted with 9 mL DCM/cyclohexane mixture (30%) in
fraction 1 (mono–ortho dl-PCBs) and 40 mL of toluene in fraction
2 (PCDDs/Fs, non-ortho dl-PCBs). Each fraction was concentrated
using the stream of nitrogen in a TurboVap II concentrator unit
(Caliper LifeSciences, USA) and transferred into an insert in a vial.
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M. Beníšek et al. / Chemosphere 122 (2015) 168–175
The sensitivity (syringe) standards (13C 1,2,3,4-TCDD and
1,2,3,7,8,9-HxCDD, 13C PCBs 70, 111, 138 and 170) were added to
all samples. The final volume prepared for analyses was 50 lL.
High resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) instrumental analysis of PCDDs/Fs and
dl-PCBs was performed on an 7890A GC (Agilent, USA) equipped
with a 60 m 0.25 mm 0.25 lm DB5-MS column (Agilent J&W,
USA) coupled to an AutoSpec Premier MS (Waters, Micromass,
UK). The MS was operated in EI + mode at the resolution of
>10 000. Detailed recoveries and limits of quantifications for
PCDDs/Fs and dioxin-like PCBs are reported in Supplementary
materials Table S2-B, S3-B.
Concentrations of co-planar PCBs and PCDD/Fs obtained from
HRGC/HRMS were multiplied by respective toxic equivalency
factors (TEFs) and expressed as upper bound TEQ values (nondetected compounds are substituted by its limit of detection for
calculation) and lower bound TEQ values (non-detected compounds are substituted by 0 for calculation). To compare the
results from the bioassay with analytical results, concentrations
of co-planar PCBs and PCDDs/Fs were multiplied with the assayspecific relative potencies for chlorinated AhR active compounds
(RePs reported by Lee et al., 2013; Behnisch, 2003) to calculate
assay-specific TEQH4IIE. Concentrations of PAHs were multiplied
by the induction equivalency factors for PAHs (IEFs reported by
Machala et al., 2001), to calculate assay-specific TEQPAH.
2.6. H4IIE-luc bioassay
H4IIE-luc, rat hepato-carcinoma cells stably transfected with
the luciferase gene under control of the arylhydrocarbon receptor
(AhR) were used for analysis of dioxin-like activity of the samples
(Giesy et al., 2002). H4IIE-luc cells were cultured in Dulbecco’s
modified Eagle medium – DMEM (PAA, Austria) with 10% fetal calf
serum in incubator with 5% CO2 at 37 °C. H4IIE-luc cells were
seeded into 96-well plates (15 000 cells per well). After 24 h, dilution series of tested samples, calibration (0.4–500 pM TCDD-doseresponse curve is shown in Supplementary materials-Fig. S1) and
negative (solvent) control were added (final concentration of the
solvent was 0.5%). Exposures were conducted in three replicates
for 24 h. After exposure to extracts of samples or standards, microscopic evaluation of each well was performed to check cytotoxic
effects and luminescence intensity was measured by use of the
Promega Steady Glo kit (Promega, Mannheim, Germany). Dioxinlike potencies were determined by use of the equi-effective
approach and the results were expressed as dioxin-like equivalents
(TEQbio) with respect to standard 2,3,7,8-tetrachlorodibenzo-pdioxin (TCDD). TEQbio was calculated from the dose-response curve
model fitted to the Hill function, based on the comparison of EC50
of standard TCDD to EC50 of samples (Villeneuve et al., 2000). All
calculations were performed in GraphPad Prism 5.0.
2.7. Statistical analysis
Correlations among the parameters were tested using the Pearson’s correlation and controlled by the non-parametric Spearman’s
R. P-values less than 0.05 were considered statistically significant.
3. Results and discussion
The chemical contamination of composts repeatedly applied on
the arable soil can have adverse effects on the quality of soils and
food chains (Déportes et al., 1995). To our knowledge, only a few
isolated studies investigated the concentrations of organic contaminants and their potential to induce dioxin-like effects in compost
samples but broader representative investigation and assessment
of the contribution of individual chemical classes to the dioxin-like
effects has been missing.
In the present study concentrations of 19 PAHs in 88 samples
were quantified, 12 of them were US EPA priority PAHs (Supplementary Table S1) and exhibited a broad range of contamination
from 1.2 102 to 2.6 104 lg kg 1, dry mass (dm) (Table 1). The
most abundant of analyzed PAHs in most of the samples were fluoranthene and pyrene (Supplementary materials Table S1). Greater
median concentrations were found in compost categories A, B, C,
H and I, while lesser concentrations were observed in other compost categories (Table 1). Several studies investigated concentrations of PAHs in composts (Table 3), and the range of PAHs
previously reported (2.7 101–2.1 104 lg kg 1, dm) well correspond to the findings of the present study. Only a single sample
(category ‘‘Others‘‘) had greater concentrations of 19 PAHs
(2.6 104 lg kg 1, dm; see Supplemental Table S1-E). The same
sample contained greater concentrations of 11 US EPA PAHs
(2.2 104 lg kg 1, dm; i.e. sum of 12 US EPA PAHs without
dibenz[a,h]anthracene), which is directly comparable to the maximum concentration of 2.1 104 lg kg 1 reported in the literature
(McGowin et al., 2001). Some limits have been suggested in the
European countries ranging from 4 to 10 mg kg 1, dm for US EPA
16 priority PAHs (Brändli et al., 2004). With the exception of the
most contaminated composts, most concentrations were less than
the limit of 10 mg kg 1, dm when 12 analyzed US EPA priority PAHs
were considered (Supplementary Table S1). Since a significant
correlation between the sums of PAH16 and PAH12 has been
previously demonstrated with an average ratio of 1.073 (Brändli
et al., 2007a), it can be concluded that most of the composts complied with the given limit value of 10 mg kg 1, dm. When compared
with the lesser suggested limit (4 mg kg 1, dm), few samples from
Table 1
Results of PAHs, TEQPAHs and TEQbio for respective groups of compounds.
Group
N
A
B
C
D
F
G
H
I
28
23
16
8
5
1
2
5
PAHs (lg kg
1
TEQPAH (lg kg
)
1
TEQbio (lg kg
)
1
)
Median
90% int
Max
Median
90% int
Max
Median
90% int
Max
1.6E+03
1.2E+03
1.3E+03
6.9E+02
9.3E+02
–
1.5E+03
1.2E+03
3.2E+03
2.9E+03
3.0E+03
1.6E+03
1.2E+03
–
1.6E+03
1.7E+04
5.5E+03
8.5E+03
1.1E+04
2.2E+03
1.2E+03
7.4E+02
1.6E+03
2.6E+04
1.7E
1.4E
1.6E
8.8E
1.0E
–
2.4E
1.4E
4.7E 01
5.4E 01
4.5E 01
1.8E 01
1.3E 01
–
2.9E 01
1.7E+00
8.3E 01
1.9E+00
2.0E+00
2.9E 01
1.3E 01
1.2E 01
3.0E 01
2.8E+00
5.7E 01
6.4E 01
5.1E 01
5.9E 01
5.0E 02
–
1.2E+00
5.6E 01
1.6E+00
1.8E+00
1.7E+00
1.1E+00
4.1E 01
–
1.2E+00
7.4E+00
3.3E+00
3.8E+00
4.4E+00
1.3E+00
4.7E 01
9.0E 02
1.3E+00
8.2E+00
01
01
01
02
01
01
01
A – biobin + green waste compost, B – green waste compost, C – sewage sludge compost, D – MBT compost, F – manure + biowaste digestate, G – manure + energy crops
digestate, H – MBT digestate, I – Other; PAH – polycyclic aromatic hydrocarbons, TEQPAH – toxic equivalent of 2,3,7,8 TCDD for PAHs calculated from analytical results and
induction equivalency factors for PAHs, TEQbio – toxic equivalent of 2,3,7,8 TCDD calculated from bioassay results.
02
02
01
02
01
02
02
02
02
02
02
02
01
01
01
02
01
9.1E
6.2E
3.3E
3.9E
1.8E
8.1E
8.8E
8.1E
9.2E
5.9E
6.7E
4.9E
2.8E
1.0E
1.9E
7.6E
3.4E
1
PeCB
(lg kg
1A
2A
3A
4A
1B
2B
1C
2C
3C
1D
2D
1F
2F
1G
1H
2H
1I
1.6E+03
1.0E+03
1.6E+03
2.6E+03
1.5E+03
4.2E+02
9.1E+03
1.4E+03
8.5E+02
6.2E+02
2.0E+03
8.3E+02
1.1E+03
6.8E+02
1.3E+03
1.2E+03
2.3E+04
1.7E+03
1.2E+03
1.7E+03
3.0E+03
1.8E+03
5.0E+02
1.1E+04
1.5E+03
9.4E+02
7.0E+02
2.2E+03
9.3E+02
1.2E+03
7.4E+02
1.6E+03
1.4E+03
2.6E+04
2.1E 01
2.0E 01
1.6E 01
3.6E 01
2.5E 01
8.5E 02
2.0E+00
1.8E 01
1.5E 01
1.1E 01
3.0E 01
1.2E 01
1.3E 01
1.2E 01
3.0E 01
1.8E 01
2.8E+00
4.1E
9.7E
2.3E
2.2E
1.3E
1.7E
4.0E
1.2E
3.4E
2.3E
4.7E
9.0E
1.4E
7.0E
7.7E
2.7E
5.4E
01
02
01
01
01
01
02
01
01
01
01
03
02
03
02
01
01
8.0E
4.5E
6.1E
7.0E
5.0E
7.7E
1.6E
9.4E
1.1E
5.5E
8.3E
1.5E
1.5E
1.9E
3.8E
7.7E
2.0E
03
03
03
03
03
03
02
03
02
03
03
02
02
02
03
03
02
3.3E+00
1.9E+00
4.2E+00
5.0E+00
2.7E+00
1.7E+00
2.0E+00
4.0E+00
6.1E+00
5.0E+00
2.2E+00
1.1E 01
1.7E+00
5.3E 01
1.4E+00
8.3E+00
4.1E+00
1.2E
8.1E
1.5E
9.3E
9.8E
1.0E
6.9E
2.4E
1.6E
6.8E
3.9E
6.0E
4.7E
2.1E
2.8E
1.0E
1.3E
03
04
03
04
04
03
02
03
03
04
04
05
04
04
04
03
03
2.7E+00
5.2E 01
3.3E+00
2.0E+00
3.8E+00
6.5E 01
4.4E+00
1.1E+00
1.8E+00
1.3E+00
9.6E 01
3.4E 01
4.6E 01
9.0E 02
1.3E+00
1.2E+00
8.2E+00
)
2.2E+01
1.8E+01
2.7E+01
4.4E+01
1.8E+01
1.5E+01
1.0E+01
3.4E+01
2.9E+01
2.1E+01
1.4E+01
9.8E 01
1.1E+01
8.5E+00
1.0E+01
3.0E+01
3.0E+01
5.6E+01
2.2E+00
1.7E+01
5.2E+00
1.2E+01
2.1E+00
1.4E+01
6.3E+00
9.7E+00
8.9E+00
6.8E+00
1.3E+00
1.6E+00
4.9E 01
1.9E+00
9.4E+00
6.8E+00
5.9E 01
7.8E 01
5.6E 01
5.5E 01
9.2E 01
5.7E 01
1.1E+01
6.0E 01
6.4E 01
5.8E+00
4.1E+00
3.4E+00
4.2E 01
5.9E 01
4.4E 01
6.1E 01
2.3E+00
3.2E 01
6.4E 01
1.1E+00
1.6E 01
4.0E 01
3.6E 01
3.9E 01
4.6E 01
2.5E 01
1.5E 01
4.7E 01
6.9E 02
3.6E 01
1.5E 01
1.5E+00
1.9E 01
5.9E+00
)
1
HCB
(lg kg
P
HCH
(lg kg 1)
P
DDT
(lg kg 1)
P
6PCB ind.
(lg kg 1)
1
TEQbio
(lg kg
TEQH4IIE DL-PCBsUB (lg kg 1)
P
DL-PCBs
(lg kg 1)
Table 2
Results of all measured chemical and biological data for 17 selected compost samples.
P
P
P
Sample
12 US-EPA PAHs
19 PAHs
TEQPAHs
PCDDs/Fs
TEQH4IIE PCDDs/Fs1
1
1
no.
(lg kg )
UB (lg kg 1)
(lg kg )
(lg kg )
(lg kg 1)
A – biobin + green waste compost, B – green waste compost, C – sewage sludge compost, D – MBT compost, F – manure + biowaste digestate, G – manure + energy crops digestate, H – MBT digestate, I – other; PAHs – polycyclic
aromatic hydrocarbons; TEQ – toxic equivalent of 2,3,7,8 tetrachlorodibenzo-p-dioxin; PCDDs/Fs – polychlorinated dibenzodioxins/furans; DL-PCB – dioxin-like polychlorinated biphenyls; DDT – dichlorodiphenyltrichloroethane;
HCB-hexachlorobenzene; PeCB – pentachlorobenzene; HCH – hexachlorocyclohexane; TEQPAH – toxic equivalent of 2,3,7,8 TCDD for PAHs calculated from analytical results and induction equivalency factors for PAHs, TEQbio – toxic
equivalent of 2,3,7,8 TCDD calculated from bioassay results; TEQH4IIE – toxic equivalent of 2,3,7,8 TCDD calculated from analytical results and relative potencies (REPs) of PCDDs/Fs or DL-PCBs.
M. Beníšek et al. / Chemosphere 122 (2015) 168–175
)
172
categories A (N = 2), B (N = 2), C (N = 1) and I (N = 1) were greater
than this more conservative criterion. In some countries limits for
PAHs consider also the sums of fewer PAHs, such as 6 PAHs with
the limit of 6 mg kg 1, dm in Austria or 11 PAHs with the limit of
3 mg kg 1, dm in Denmark (Brändli et al., 2004).
A subset of seventeen samples was further analyzed for organochlorine compounds (Table 2). Among PCDDs/Fs and dioxin-like
PCBs, the most abundant congener was OCDD, followed by
1,2,3,4,6,7,8 HpCDD (Supplementary materials – Table S2-A).
Concentrations of TEQ, based on concentrations of the PCDDs/Fs,
ranged from 2.9 to 15.1 ng WHO-TEQ kg 1, dm. Compared to concentrations in the literature (Table 3), similar concentrations were
reported by Brändli et al. (2007b), lesser values were measured by
Muñoz et al. (2013), and greater TEQs were found in an older study
from Brazil (Grossi et al., 1998). Various values for quality limits
have been accepted in different countries ranging from 20 ng International TEQ kg 1, dm (I-TEQ) in Switzerland (Brändli et al., 2004)
to 100 ng I-TEQ kg 1, dm in Belgium (Tavazzi et al., 2013; Saveyn
and Eder, 2014). In all cases concentrations of TEQ were less than
the conservative limits, with a maximum measured concentration
of 15 ng WHO-TEQ kg 1, dm (or 14 ng I-TEQ kg 1, dm; Supplementary Table S2-A) confirming thus again generally good quality of
European composts.
The contribution of dioxin-like PCBs to TEQs was less than that
of PCDDs/Fs (Table 2), with the exception of a sample 1C, which
had relatively great concentrations of PCB 126 (70 ng dl-PCB
TEQ kg 1, dm; Table 2 and Supplementary Table S3-A). Upper
bound concentrations in other samples ranged from 0.1 to
2.5 ng dl-PCB TEQ kg 1, dm. These are comparable to values available in the literature, which ranged from 0.4 to 6.8 ng TEQ kg 1, dm
(Brändli et al., 2007b) (Table 3).
Concentrations of six indicator PCBs ranged from 1 to
44 lg kg 1, dm (Table 2, Supplementary Table S4) with PCB 153,
138 and 180 being the most abundant congeners. Concentrations
in the present study were less than those in another European
study (Lazzari et al., 1999), which ranged from 1.4 101 to
1.3 102 lg kg 1, dm, and less than the most conservative limit
of 80 lg kg 1, dm used in Denmark (Tavazzi et al., 2013). Also for
congener PCBs limits vary among countries from 80 lg kg 1 to
800 lg kg 1, dm for PCB7 and from 1 102 to 1 103 lg kg 1,
dm for PCB6, respectively (Tavazzi et al., 2013). Concentrations of
organochlorine pesticides are given in Table 2. Sum of DDTs ranged
from 0.49 to 56 lg kg 1, dm, while maximum concentrations of
HCH (sum of congeners), HCB and PeCB were 11, 5.9 and
0.3 lg kg 1, dm, respectively. Only limited comparable data could
be found in the literature but similar mean concentrations of sums
of DDTs and HCHs (about 18 and 3.5 lg kg 1, dm, respectively)
were reported by Brändli et al. (2004). The same study found
slightly greater mean concentrations of PeCB (mean 1.2 lg kg 1,
dm). In summary, analyses of several classes of chemical contaminants revealed good compliance of the studied composts with
the limits available for POPs or PAHs.
The in vitro H4IIE-luc bioassay revealed significant biological
activities with the effective concentrations ranging from 0.5 to
1.2 lg TEQbio kg 1, dm for most of the categories (Table 1). The
observed effects were comparable available literature (Table 3,
Takigami et al., 2010).
Lesser concentrations were found in category F (digestates from
manure and source separated biowaste) with a median concentration of 0.05 lg TEQbio kg 1, dm, while greater concentrations were
detected in category I (‘‘Others’’) (maximum 8.22 lg TEQbio kg 1,
dm, which included some bark and municipal waste composts –
Supplementary materials-Table S5). A subset of 17 samples was
further tested after a treatment with sulfuric acid, which substantially reduced AhR-effects, and only a single sample (No. 3C)
induced an AhR-mediated response near to the limit of detection
173
M. Beníšek et al. / Chemosphere 122 (2015) 168–175
Table 3
Comparison of the results with literature.
This study
Literature values
2
4
PAHs
1.2 10 –2.6 10 lg kg
PCDDs/Fs
3–15 ng WHO–TEQ kg
DL-PCBs
0.8–70 ng WHO TEQ kg
TEQ bio
<10 ng kg
Ind. PCBs
1–44 lg kg
1
1
1
upper bound
1
upper bound
–8.2 103 ng kg
1
P
( 19 PAHs)
1
References
P
2.1 10 –1.1 10 lg kg ( 15 PAHs)
2
4
1 P
4 10 –2.1 10 lg kg ( 11 PAHs)
P
27–2.1 102 lg kg 1 ( 16 PAHs)
Grossi et al. (1998)
McGowin et al. (2001)
Takigami et al. (2010)
3–1.6 102 ng I-TEQ kg 1
0.52–21 ng I-TEQ kg 1
0.25–2.5 ng WHO TEQ kg 1
Grossi et al. (1998))
Brändli et al. (2007b)
Muñoz et al. (2013)
2
4
1
0.4–6.8 ng WHO–TEQ kg
1
Brändli et al. (2007b)
22–3.9 103 ng kg
360 ng kg 1
1
Takigami et al. (2010)
Suzuki et al. (2006)
14–1.3 102 lg kg
1
Lazzari et al. (1999)
PAHs – polycyclic aromatic hydrocarbons; PCDDs/Fs – polychlorinated dibenzodioxins/furans; DL-PCB – dioxin-like polychlorinated biphenyls; TEQbio – toxic equivalent of
2,3,7,8 tetrachlorodibenzo-p-dioxin calculated from bioassay; Ind. PCBs – indicator polychlorinated biphenyls.
Fig. 1. Correlation between TEQPAH and TEQbio. (A) biobin + green waste compost, (B) green waste compost, (C) sewage sludge compost, (D) MBT compost, (E) all parallel data
(TEQPAH and TEQbio); TEQPAH – toxic equivalent of 2,3,7,8 TCDD for PAHs calculated from analytical results and induction equivalency factors for PAHs, TEQbio-toxic equivalent
of 2,3,7,8 TCDD calculated from bioassay results; RP – Pearson’s correlation, RS – Spearman’s correlation, ns – not significant.
174
M. Beníšek et al. / Chemosphere 122 (2015) 168–175
(LOD) TEQbio – 10 ng TEQbio kg 1, dm. Dose-response curves of raw
extract and sulfuric acid treated extract of the sample 3C are presented in Supplementary materials-Fig. S1.
Comparison of TEQbio and TEQPAH indicated that in some samples PAHs were likely responsible for the majority of the dioxinlike effects since concentrations of TEQPAH were even greater than
TEQbio (N = 4 samples from category A, N = 2 from category F, N = 1
from categories C and G, see Supplementary materials Table S5). In
most of the samples (N = 80) concentrations of TEQPAH calculated
from RePs and concentrations of measured PAHs could account
for 10–90% of TEQbio. Statistically significant correlations between
P
TEQbio and TEQPAH were observed (Spearman’s R, p < 0.05, Fig. 1),
and the correlations were also significant for the subset of 17 samples (Pearson P < 0.0001; Spearman P = 0.007). Contrary, correlations between TEQbio in crude extracts and calculated TEQs based
on PCDDs/Fs and dioxin-like PCBs TEQs were not significant
(Spearman’s R, p > 0.05) confirming again the importance of PAHs
for dioxin-like effects. Comparison with the chemical analyses
showed that benzo(k)fluoranthene and dibenz(a,h)anthracene
were the greatest contributors to the observed dioxin-like activity.
Although PAHs seem to be important chemicals causing dioxinlike effects not only in composts but also in sediments (Hilscherova
et al., 2001), results of some other studies have indicated they may
have a relatively minor role. For example Takigami et al. (2010)
estimated the proportion of TEQ contributed by PAHs compost
being only 0.2–1.8%, and the same study also confirmed minor
contributions of persistent compounds that accounted for maximum 0.3% of the total TEQbio in crude extracts These findings, also
in agreement with other studies focusing e.g. on sediments
(Hilscherova et al., 2001), indicate the toxicological importance of
other non-analyzed chemicals, which could be detected only by
the biological assay such as heterocyclic PAHs (Sovadinova et al.,
2006) or diverse metabolites of PAHs such as hydroxides and epoxides (Jeuken et al., 2003).
4. Conclusions
Analyses of a unique set of European compost samples (88
samples from 16 European countries, 8 different types/categories)
indicate that in the regulatory controlled parameters, such as concentrations of PAHs, PCDD/Fs, PCBs or TEQs, few of the samples
exceeded the most conservative limits applied within different
countries. The values found in the composts were in general agreement with other previously published studies. The results of the
effect-based analyses, using the in vitro test for dioxin-like effects,
were correlated with concentrations of PAHs. However, persistent
dioxin-active compounds such as PCDDs/Fs and dioxin-like PCBs
were detected at generally small concentrations and did not significantly contribute to the observed dioxin-like effects. The present
study provides one of few comprehensive investigations of the
compost contamination by organic contaminants and shows generally good quality of the composts at the European level (with
respect to chemical contamination by traditionally analyzed PAHs
and POPs). The study also demonstrates the need to introduce the
effect-based monitoring of the complex contaminated samples,
and derive corresponding effect-based trigger values as also suggested for other environmental matrices (Tang et al., 2013).
Acknowledgements
The research was supported by the European Social Fund, the
state budget of the Czech Republic, and by the grants from the
Ministry of Education of the Czech Republic (LM2011028 and
LO1214). It was performed in the framework of the end-of-waste
project of the EU (http://susproc.jrc.ec.europa.eu/activities/waste/
). Prof. Giesy was supported by the Canada Research Chair program, a Visiting Distinguished Professorship in the Department of
Biology and Chemistry and State Key Laboratory in Marine Pollution, City University of Hong Kong, the 2012 ‘‘Great Concentration
Foreign Experts’’ (#GDM20123200120) program, funded by the
State Administration of Foreign Experts Affairs, the P.R. China to
Nanjing University and the Einstein Professor Program of the Chinese Academy of Sciences.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.chemosphere.
2014.11.039.
References
Behnisch, P., 2003. Brominated dioxin-like compounds: in vitro assessment in
comparison to classical dioxin-like compounds and other polyaromatic
compounds. Environ. Int. 29, 861–877.
Brändli, R., Kupper, T., Bucheli, T., Mayer, J., Stadelmann, F.X., Tarradellas, J., 2004.
Occurrence and relevance of organic pollutants in compost, digestate and
organic residues – literature review. Agroscope FAL/Reckenholz/EPF Lausanne/
ENAC/ISTE/CECOTOX. p. 193. (<http://www.bafu.admin.ch/abfall/01472/01480/
01742/index.html?lang=en>).
Brändli, R.C., Bucheli, T.D., Kupper, T., Furrer, R., Stahel, W.A., Stadelmann, F.X.,
Tarradellas, J., 2007a. Organic pollutants in compost and digestate. Part 1.
Polychlorinated biphenyls, polycyclic aromatic hydrocarbons and molecular
markers. J. Environ. Monit. 9, 456–464.
Brändli, R.C., Kupper, T., Bucheli, T.D., Zennegg, M., Huber, S., Ortelli, D., Müller, J.,
Schaffner, C., Iozza, S., Schmid, P., Berger, U., Edder, P., Oehme, M., Stadelmann,
F.X., Tarradellas, J., 2007b. Organic pollutants in compost and digestate. Part 2.
Polychlorinated dibenzo-p-dioxins, and -furans, dioxin-like polychlorinated
biphenyls, brominated flame retardants, perfluorinated alkyl substances,
pesticides, and other compounds. J. Environ. Monit. 9, 465–472.
Déportes, I., Benoit-Guyod, J.-L., Zmirou, D., 1995. Hazard to man and the
environment posed by the use of urban waste compost: a review. Sci. Total
Environ., 197–222.
Escher, B.I., van Daele, C., Dutt, M., Tang, J.Y.M., Altenburger, R., 2013. Most
oxidative stress response in water samples comes from unknown chemicals:
the need for effect-based water quality trigger values. Environ. Sci. Technol. 47,
7002–7011.
Giesy, J.P., Hilscherova, K., Jones, P.D., Kannan, K., Machala, M., 2002. Cell bioassays
for detection of aryl hydrocarbon (AhR) and estrogen receptor (ER) mediated
activity in environmental samples. Mar. Pollut. Bull. 45, 3–16.
Grossi, G., Lichtig, J., Kraub, P., 1998. PCDD/F, PCB and PAH content of Brazilian
compost. Chemosphere 37, 2153–2160.
Hecker, M., Giesy, J.P., 2011. Effect-directed analysis of Ah-receptor mediated
toxicants, mutagens and endocrine disruptors in sediments and biota. In: Brac,
W. (Ed.), Eff. Anal. Complex Environ. Contam., vol. 15. Springer, Berlin
Heidelberg, pp. 285–313.
Hilscherova, K., Kannan, K., Kang, Y.S., Holoubek, I., Machala, M., Masunaga, S.,
Nakanishi, J., Giesy, J.P., 2001. Characterization of dioxin-like activity of
sediments from a Czech river basin. Environ. Toxicol. Chem. 20, 2768–2777.
Hseu, Z.-Y., 2004. Evaluating heavy metal contents in nine composts using four
digestion methods. Bioresour. Technol. 95, 53–59.
ISO, 2014. ISO (2014) NWIP ISO/NP 19040–3 – Water quality – determination of the
estrogenic potential of water and waste water – Part 3: in vitro human cellbased reporter gene assay [draft norm in the validation process].
Jeuken, A., Keser, B.J.G., Khan, E., Brouwer, A., Koeman, J., Denison, M.S., 2003.
Activation of the Ah receptor by extracts of dietary herbal supplements,
vegetables, and fruits. J. Agric. Food Chem. 51, 5478–5487.
Joung, K.E., Chung, Y.H., Sheen, Y.Y., 2007. DRE-CALUX bioassay in comparison with
HRGC/MS for measurement of toxic equivalence in environmental samples. Sci.
Total Environ. 372, 657–667.
Lasaridi, K., Protopapa, I., Kotsou, M., Pilidis, G., Manios, T., Kyriacou, A., 2006.
Quality assessment of composts in the Greek market: the need for standards
and quality assurance. J. Environ. Manage. 80, 58–65.
Lazzari, L., Sperni, L., Salizzato, M., Pavoni, B., 1999. Gas chromatographic
determination of organic micropollutants in samples of sewage sludge and
compost: behaviour of PCB and PAH during composting. Chemosphere 38,
1925–1935.
Lee, K.T., Hong, S., Lee, J.S., Chung, K.H., Hilscherová, K., Giesy, J.P., Khim, J.S., 2013.
Revised relative potency values for PCDDs, PCDFs, and non-ortho-substituted
PCBs for the optimized H4IIE-luc in vitro bioassay. Environ. Sci. Pollut. Res. Int.
20, 8590–8599.
Machala, M., Vondráček, J., Bláha, L., Ciganek, M., Neča, J., 2001. Aryl hydrocarbon
receptor-mediated activity of mutagenic polycyclic aromatic hydrocarbons
determined using in vitro reporter gene assay. Mutat. Res. Toxicol. Environ.
Mutagen. 497, 49–62.
M. Beníšek et al. / Chemosphere 122 (2015) 168–175
McGowin, A.E., Adom, K.K., Obubuafo, A.K., 2001. Screening of compost for PAHs
and pesticides using static subcritical water extraction. Chemosphere 45, 857–
864.
Mrema, E.J., Rubino, F.M., Brambilla, G., Moretto, A., Tsatsakis, A.M., Colosio, C.,
2013. Persistent organochlorinated pesticides and mechanisms of their toxicity.
Toxicology 307, 74–88.
Muñoz, M., Gomez-Rico, M.F., Font, R., 2013. Dioxin-like PCB concentrations during
municipal solid waste biomethanation and subsequent composting.
Chemosphere.
Murk, A.J., Legler, J., Denison, M.S., Giesy, J.P., van de Guchte, C., Brouwer, A., 1996.
Chemical-activated luciferase gene expression (CALUX): a novel in vitro
bioassay for Ah receptor active compounds in sediments and pore water.
Fundam. Appl. Toxicol. 33, 149–160.
Pedra, F., Polo, A., Ribeiro, A., Domingues, H., 2007. Effects of municipal solid waste
compost and sewage sludge on mineralization of soil organic matter. Soil Biol.
Biochem. 39, 1375–1382.
Samara, F., Gullett, B.K., Harrison, R.O., Chu, A., Clark, G.C., 2009. Determination of
relative assay response factors for toxic chlorinated and brominated dioxins/
furans using an enzyme immunoassay (EIA) and a chemically-activated
luciferase gene expression cell bioassay (CALUX). Environ. Int. 35, 588–593.
Saveyn, H., Eder, P., 2014. End-of-waste criteria for biodegradable waste subjected
to biological treatment (compost & digestate): Technical proposal. EC JRC
Scientific and Policy Reports (EUR 26425 EN).
Semple, K., 2001. Impact of composting strategies on the treatment of soils
contaminated with organic pollutants. Environ. Pollut. 112, 269–283.
Sorg, O., 2013. AhR signalling and dioxin toxicity. Toxicol. Lett.. http://dx.doi.org/
10.1016/j.toxlet.2013.10.039.
Sovadinova, I., Blaha, L., Janosek, J., Hilscherova, K., Giesy, J.P., Jones, P.D., Holoubek,
I., 2006. Cytotoxicity and aryl hydrocarbon receptor-mediated activity of
175
N-heterocyclic
polycyclic
aromatic
hydrocarbons:
structure-activity
relationships. Environ. Toxicol. Chem. 25, 1291–1297.
Suzuki, G., Takigami, H., Kushi, Y., Sakai, S., 2006. Time-course changes of mixture
effects on AhR binding-dependent luciferase activity in a crude extract from a
compost sample. Toxicol. Lett. 161, 174–187.
Takigami, H., Suzuki, G., Sakai, S., 2010. Screening of dioxin-like compounds in biocomposts and their materials: chemical analysis and fractionation-directed
evaluation of AhR ligand activities using an in vitro bioassay. J. Environ. Monit.
12, 2080–2087.
Tang, J.Y.M., McCarty, S., Glenn, E., Neale, P.A., Warne, M.S.J., Escher, B.I., 2013.
Mixture effects of organic micropollutants present in water: towards the
development of effect-based water quality trigger values for baseline toxicity.
Water Res. 47, 3300–3314.
Tavazzi, S., Locoro, G., Comero, S., Sobiecka, E., Loos, R., Eder, P., Saveyn, H., Blaha, L.,
Benisek, M., Gans, O., Hartl, W., Voorspoels, S., Ghiani, M., Umlauf, G., Mariani,
G., Suurkuusk, G., Paracchini, B., Cristache, C., Fissiaux, I., Alonzo-Ruiz, A.,
Gawlik, B., 2013. Occurrence and levels of selected compounds in European
compost and digestate samples. European Commission – Joint Research Centre,
JRC Scientific and Policy Reports (EUR 26164 EN/ISBN 978-92-79-33195-4).
Umlauf, G., Christoph, E.H., Lanzini, L., Savolainen, R., Skejo, H., Bidoglio, G.,
Clemens, J., Goldbach, H., Scherer, H., 2011. PCDD/F and dioxin-like PCB profiles
in soils amended with sewage sludge, compost, farmyard manure, and mineral
fertilizer since 1962. Environ. Sci. Pollut. Res. Int. 18, 461–470.
Villeneuve, D., Blankenship, A., Giesy, J., 2000. Derivation and application of relative
potency estimates based on in vitro bioassay results. Environ. Toxicol. Chem. 19,
2835–2843.
WRAP, 2002. The Waste and Resources Action Program (WRAP): Comparison of
Compost Standards within the EU, North America and Australasia. Main reportsection 1, WRAP, Banbury.
SUPPLEMENTARY MATERIALS:
Dioxins and dioxin-like compounds in composts and digestates from European countries as determined by the in vitro bioassay and
chemical analysis
Martin Beníšek1, Petr Kukučka1, Giulio Mariani2, Gert Suurkuusk2, Bernd M. Gawlik2, Giovanni Locoro2, John P. Giesy3,4,5,6, Luděk Bláha1*
1- Masaryk University, Faculty of Science, RECETOX
2-European Commission, DG Joint Research Centre (JRC), Institute for Environment and Sustainability,Unit H.01-Water Resources Unit, Ispra,
Italy
3- Department of Veterinary Biomedical sciences and Toxicology Centre, University of Saskatchewan, SK, Canada
4- Department of Biology & Chemistry and State Key Laboratory in Marine Pollution, City University of Hong Kong, Kowloon, Hong Kong,
SAR, China
5- School of Biological Sciences, University of Hong Kong, Hong Kong, SAR, China
6- State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, People’s Republic
of China
* corresponding author
Table S1-A – Results of PAHs measurement for biobin+greenwaste compost (type A)-samples 1-14
Location Code
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Type
A
A
A
A
A
A
A
A
A
A
A
A
A
A
Belgium
France
France
Finland
Italy
Luxembourg
Belgium
Netherland
Spain
Sweden
Netherland
Denmark
Germany
Germany
Phenantrene*
5.2E+02
4.3E+01
6.0E+02
5.0E+01
4.1E+02
1.2E+01
2.2E+01
4.1E+02
8.3E+01
2.9E+01
1.5E+02
1.4E+02
3.3E+02
1.2E+01
Antracene*
9.4E+00
4.2E+01
4.2E+01
7.3E+00
3.1E+00
2.7E+01
1.6E+01
8.3E+01
4.6E+00
2.6E+01
4.8E+01
1.2E+01
1.4E+01
1.1E+01
Fluoranthene*
1.0E+03
7.9E+01
6.5E+02
1.0E+02
2.5E+02
1.4E+02
4.3E+02
7.8E+02
8.9E+01
1.4E+02
5.9E+02
1.7E+02
4.0E+02
2.1E+02
Pyrene*
5.9E+02
4.4E+01
3.7E+02
5.7E+01
1.3E+02
1.2E+02
2.9E+02
4.4E+02
7.8E+01
8.5E+01
4.5E+02
1.3E+02
2.4E+02
1.5E+02
Benzo(a)antracene*
8.5E+01
1.7E+01
1.3E+02
1.0E+01
2.7E+01
2.0E+02
1.1E+02
1.4E+02
1.9E+01
4.3E+01
1.3E+02
3.0E+01
7.1E+01
7.9E+01
Chrysene*
4.5E+02
2.5E+01
2.1E+02
1.3E+01
4.5E+03
3.6E+02
2.3E+02
2.0E+02
2.4E+01
7.2E+01
2.0E+02
4.8E+01
1.2E+02
1.3E+02
Benzo(b)fluoranthene*
4.1E+02
2.3E+01
1.2E+02
2.2E+01
3.7E+01
2.8E+02
1.5E+02
1.9E+02
2.3E+01
4.0E+01
1.1E+02
4.2E+01
7.9E+01
1.3E+02
Benzo(k)fluoranthene*
1.9E+02
1.4E+01
6.1E+01
1.6E+01
2.2E+01
1.4E+02
6.4E+01
8.1E+01
2.2E+01
2.1E+01
5.3E+01
2.6E+01
3.9E+01
6.5E+01
Benzo(e)pyrene
2.7E+02
1.9E+01
8.6E+01
1.6E+01
2.5E+01
2.2E+02
1.1E+02
1.3E+02
2.7E+00
2.3E+01
8.3E+01
4.0E+01
5.5E+01
8.9E+01
Benzo(a)pyrene*
2.4E+02
1.3E+01
3.9E+01
9.7E+00
2.8E+00
1.5E+02
5.3E+01
1.2E+02
2.8E+00
1.2E+01
6.3E+01
2.5E+01
3.6E+01
6.0E+01
Perylene
4.0E+01
1.4E+01
2.9E+01
1.7E+01
3.1E+00
5.8E+01
2.6E+01
5.0E+01
3.1E+00
1.0E+01
3.1E+01
1.8E+01
2.6E+01
4.7E+01
Indeno(1,2,3-cd)pyrene*
2.9E+02
4.9E+01
6.1E+01
1.9E+01
2.8E+01
1.6E+02
6.7E+01
1.3E+02
3.0E+00
1.9E+01
5.9E+01
2.7E+01
6.0E+01
7.0E+01
Dibenz(a,h)antracene*
9.7E+01
3.2E+00
4.4E+01
3.2E+00
3.2E+00
9.7E+01
4.2E+01
3.2E+00
3.2E+00
1.4E+01
3.8E+01
1.5E+01
3.0E+01
4.4E+01
Benzo(g,h,i)perylene*
2.8E+02
3.4E+00
7.3E+01
1.4E+01
3.4E+00
2.0E+02
8.7E+01
9.9E+01
2.4E+01
2.5E+01
7.2E+01
2.8E+01
7.0E+01
7.9E+01
Dibenzo(a,l)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,h)pyrene
4.6E+02
BLOQ
BLOQ
BLOQ
BLOQ
1.1E+02
BLOQ
BLOQ
BLOQ
BLOQ
1.8E+01
BLOQ
BLOQ
BLOQ
Dibenzo(a,i)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,e)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Coronene
1.1E+02
5.7E+00
4.7E+01
5.7E+00
5.7E+00
7.1E+01
5.7E+00
5.7E+00
5.7E+00
5.7E+00
1.7E+01
5.7E+00
5.7E+00
5.7E+00
∑ all 19 PAHs (µg/kg dm)
5.1E+03
3.9E+02
2.6E+03
3.6E+02
5.5E+03
2.4E+03
1.7E+03
2.9E+03
3.9E+02
5.7E+02
2.1E+03
7.5E+02
1.6E+03
1.2E+03
∑12 EPA PAHs (µg/kg dm)
4.2E+03
3.5E+02
2.4E+03
3.2E+02
5.4E+03
1.9E+03
1.6E+03
2.7E+03
3.7E+02
5.3E+02
2.0E+03
6.9E+02
1.5E+03
1.0E+03
TEQPAH (µg/kg dm)
6.0E-01
4.5E-02
2.0E-01
3.9E-02
5.0E-01
4.5E-01
2.1E-01
2.1E-01
4.4E-02
6.7E-02
1.8E-01
7.7E-02
1.4E-01
2.0E-01
Country of origin
PAH (µg/kg dm)
Summaries
Table S1 –A - Results of PAHs measurement for biobin+greenwaste compost (type A)-samples 15-28
Location Code
15
16
17
18
19
20
21
22
23
24
25
26
27
28
Type
A
A
A
A
A
A
A
A
A
A
A
A
A
A
Germany
Germany
France
Germany
Italy
Italy
Italy
Portugal
Belgium
UK
Suisse
Suisse
Germany
Belgium
Phenantrene*
8.6E+01
2.6E+01
5.0E+02
1.2E+02
4.5E+01
1.3E+02
1.6E+02
6.6E+01
3.1E+02
8.7E+01
1.1E+02
2.5E+02
2.4E+02
5.8E+01
Antracene*
2.6E+01
1.2E+01
1.0E+02
3.3E+01
4.9E+00
1.2E+01
3.9E+00
3.6E+00
3.5E+01
1.5E+01
2.6E+01
2.9E+01
2.9E+01
2.8E+01
Fluoranthene*
3.9E+02
6.9E+01
6.7E+02
2.7E+02
1.2E+02
2.4E+02
1.6E+02
1.2E+02
4.2E+02
1.8E+02
1.8E+02
2.8E+02
4.5E+02
7.0E+02
Pyrene*
2.6E+02
3.4E+01
4.4E+02
1.9E+02
1.0E+02
2.0E+02
1.7E+02
9.5E+01
2.5E+02
1.9E+02
1.3E+02
2.4E+02
2.6E+02
4.8E+02
Benzo(a)antracene*
9.6E+01
2.0E+02
2.0E+02
1.1E+02
2.5E+01
5.4E+01
2.9E+01
1.7E+01
8.1E+01
6.4E+02
7.4E+01
7.6E+01
9.2E+01
2.0E+02
Chrysene*
1.4E+02
3.6E+02
2.7E+02
1.6E+02
5.2E+01
9.0E+01
7.4E+01
4.6E+01
1.4E+02
1.2E+02
1.0E+02
1.1E+02
1.4E+02
3.5E+02
Benzo(b)fluoranthene*
9.1E+01
5.5E+02
2.0E+02
1.3E+02
4.2E+01
6.4E+01
3.1E+01
2.9E+01
9.9E+01
1.1E+02
1.0E+02
1.0E+02
9.8E+01
2.5E+02
Benzo(k)fluoranthene*
4.3E+01
2.5E+02
9.1E+01
7.1E+01
2.2E+01
3.6E+01
1.2E+01
1.5E+01
4.8E+01
5.0E+01
5.4E+01
5.9E+01
4.6E+01
1.2E+02
Benzo(e)pyrene
6.6E+01
3.7E+02
1.4E+02
9.5E+01
3.6E+01
5.2E+01
2.5E+01
2.4E+01
7.1E+01
9.0E+01
8.9E+01
8.2E+01
7.0E+01
2.0E+02
Benzo(a)pyrene*
4.6E+01
4.0E+02
1.2E+02
8.9E+01
2.6E+01
4.1E+01
2.8E+00
1.6E+01
4.7E+01
6.4E+01
8.2E+01
6.7E+01
5.3E+01
1.3E+02
Perylene
2.7E+01
1.6E+02
3.5E+01
4.8E+01
1.8E+01
2.3E+01
3.1E+00
1.2E+01
2.6E+01
2.5E+01
3.5E+01
3.6E+01
2.2E+01
4.4E+01
Indeno(1,2,3-cd)pyrene*
5.2E+01
3.8E+02
9.9E+01
1.0E+02
3.4E+01
7.1E+01
1.9E+01
5.4E+01
5.4E+01
7.7E+01
7.8E+01
6.1E+02
4.7E+01
1.4E+02
Dibenz(a,h)antracene*
3.2E+00
1.8E+02
6.0E+01
3.2E+00
1.7E+01
1.5E+01
8.0E+00
1.3E+01
3.4E+01
3.4E+01
3.8E+01
4.0E+01
3.1E+01
5.7E+01
Benzo(g,h,i)perylene*
6.1E+01
3.7E+02
1.2E+02
1.0E+02
4.0E+01
4.2E+01
3.5E+01
3.7E+01
4.9E+01
1.1E+02
9.7E+01
8.4E+01
6.6E+01
1.3E+02
Dibenzo(a,l)pyrene
BLOQ
BLOQ
9.8E+00
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,h)pyrene
BLOQ
BLOQ
5.5E+01
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
3.2E+01
4.5E+01
BLOQ
BLOQ
7.2E+01
Dibenzo(a,i)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,e)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Coronene
5.7E+00
5.7E+00
5.2E+01
5.7E+00
1.0E+01
2.0E+01
1.8E+01
2.1E+01
5.7E+00
6.2E+01
4.1E+01
2.4E+01
3.8E+01
6.1E+01
∑ all 19 PAHs (µg/kg dm)
1.4E+03
3.4E+03
3.2E+03
1.5E+03
6.0E+02
1.1E+03
7.5E+02
5.7E+02
1.7E+03
1.9E+03
1.3E+03
2.1E+03
1.7E+03
3.0E+03
∑12 EPA PAHs (µg/kg dm)
1.3E+03
2.8E+03
2.9E+03
1.4E+03
5.3E+02
9.9E+02
7.1E+02
5.1E+02
1.6E+03
1.7E+03
1.1E+03
2.0E+03
1.6E+03
2.6E+03
TEQPAH (µg/kg dm)
1.1E-01
8.3E-01
3.0E-01
1.8E-01
7.5E-02
1.1E-01
4.3E-02
6.3E-02
1.6E-01
1.7E-01
1.8E-01
3.5E-01
1.5E-01
3.6E-01
Country of origin
PAH (µg/kg dm)
Summaries
Table S1-B Results of PAHs measurement for greenwaste compost (Type B)-samples 1-12
Location Code
1
2
3
4
5
6
7
8
9
10
11
12
Type
B
B
B
B
B
B
B
B
B
B
B
B
Belgium
France
Luxembourg
Belgium
Netherland
Netherland
Spain
Sweden
Denmark
Germany
Germany
France
Phenantrene*
3.5E+02
1.1E+01
2.1E+01
1.6E+02
4.6E+00
1.5E+02
6.8E+01
5.9E+01
9.7E+00
4.5E+01
8.4E+00
8.8E+01
Antracene*
8.8E+01
1.3E+01
1.7E+02
3.1E+01
4.6E+00
3.2E+01
1.3E+01
2.6E+01
3.8E+00
1.5E+01
2.6E+00
2.3E+01
Fluoranthene*
6.6E+02
1.7E+02
3.4E+02
2.9E+02
2.6E+01
2.5E+02
1.2E+02
1.1E+02
7.1E+01
1.0E+02
4.1E+01
1.9E+02
Pyrene*
3.2E+02
7.7E+01
2.6E+02
2.0E+02
1.9E+01
1.7E+02
9.1E+01
8.2E+01
4.4E+01
2.9E+01
2.4E+01
1.5E+02
Benzo(a)antracene*
1.4E+02
4.8E+01
5.4E+02
9.0E+01
3.5E+01
7.5E+01
2.3E+01
5.0E+01
1.9E+01
3.8E+01
2.1E+01
7.3E+01
Chrysene*
2.4E+02
8.6E+01
7.1E+02
1.7E+02
7.8E+01
1.4E+02
3.8E+01
9.2E+01
5.1E+01
9.6E+01
7.9E+01
1.3E+02
Benzo(b)fluoranthene*
1.5E+02
7.2E+01
7.3E+02
1.5E+02
6.1E+01
1.3E+02
2.0E+01
8.9E+01
4.4E+01
1.0E+02
7.8E+01
1.1E+02
Benzo(k)fluoranthene*
7.2E+01
4.2E+01
3.5E+02
7.3E+01
2.9E+01
5.6E+01
1.0E+01
4.1E+01
2.1E+01
4.2E+01
2.5E+01
5.1E+01
Benzo(e)pyrene
9.6E+01
5.6E+01
5.1E+02
1.0E+02
3.8E+01
9.9E+01
1.5E+01
7.4E+01
3.5E+01
7.3E+01
5.4E+01
7.9E+01
Benzo(a)pyrene*
7.6E+01
4.4E+01
5.3E+02
8.6E+01
2.8E+00
7.5E+01
1.7E+01
6.4E+01
2.4E+01
4.7E+01
3.4E+01
5.4E+01
Perylene
3.7E+01
2.1E+01
2.0E+02
8.1E+00
3.1E+00
3.5E+01
5.4E+00
2.8E+01
1.2E+01
2.3E+01
1.8E+01
2.3E+01
Indeno(1,2,3-cd)pyrene*
7.5E+01
5.7E+01
4.2E+02
9.2E+01
3.4E+01
7.4E+01
1.2E+01
6.6E+01
2.8E+01
7.1E+01
3.9E+01
6.6E+01
Dibenz(a,h)antracene*
3.0E+01
3.2E+00
2.7E+02
5.9E+01
3.2E+00
4.1E+01
4.5E+00
3.5E+01
9.3E+00
3.2E+00
1.6E+01
4.2E+01
Benzo(g,h,i)perylene*
8.6E+01
4.9E+01
4.7E+02
1.2E+02
3.6E+01
9.4E+01
2.5E+01
8.2E+02
2.7E+01
7.4E+01
4.9E+01
9.0E+01
Dibenzo(a,l)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,h)pyrene
BLOQ
BLOQ
7.9E+02
1.1E+02
BLOQ
BLOQ
BLOQ
3.1E+01
BLOQ
BLOQ
BLOQ
3.2E+01
Dibenzo(a,i)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,e)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Coronene
5.7E+00
5.7E+00
1.4E+02
3.3E+01
5.7E+00
2.3E+01
1.2E+01
3.9E+01
5.7E+00
5.7E+00
5.7E+00
3.9E+01
∑ all 19 PAHs (µg/kg dm)
2.4E+03
7.5E+02
6.4E+03
1.8E+03
3.8E+02
1.5E+03
4.8E+02
1.7E+03
4.0E+02
7.7E+02
5.0E+02
1.2E+03
∑12 EPA PAHs (µg/kg dm)
2.3E+03
6.7E+02
4.8E+03
1.5E+03
3.3E+02
1.3E+03
4.5E+02
1.5E+03
3.5E+02
6.6E+02
4.2E+02
1.1E+03
TEQPAH (µg/kg dm)
2.1E-01
1.1E-01
1.2E+00
2.5E-01
7.1E-02
1.9E-01
3.2E-02
1.5E-01
6.2E-02
1.1E-01
8.5E-02
1.7E-01
Country of origin
PAH (µg/kg dm)
Summaries
Table S1-B Results of PAHs measurement for greenwaste kompost (Type B)-Samples 13-23
Location Code
13
14
15
16
17
18
19
20
21
22
23
Type
B
B
B
B
B
B
B
B
B
B
B
France
France
France
France
France
France
Belgium
Belgium
Suisse
Italy
France
Phenantrene*
1.8E+01
6.6E+01
4.5E+02
7.8E+01
1.0E+01
1.9E+01
3.4E+01
2.1E+02
7.6E+01
3.0E+01
5.0E+01
Antracene*
2.5E+01
4.4E+01
2.3E+01
1.6E+01
1.1E+01
4.6E+01
2.0E+01
9.0E+01
1.4E+01
2.7E+00
4.1E+00
Fluoranthene*
1.1E+02
1.8E+02
3.4E+02
3.6E+02
3.8E+01
4.5E+01
5.5E+02
5.0E+02
1.4E+02
3.7E+01
9.1E+01
Pyrene*
9.5E+01
1.1E+02
1.9E+02
2.2E+02
2.4E+01
2.7E+01
2.6E+02
3.4E+02
9.5E+01
3.2E+01
4.4E+01
Benzo(a)antracene*
5.5E+01
1.2E+02
6.5E+01
7.4E+01
2.8E+01
3.7E+01
1.1E+02
5.7E+02
4.4E+01
1.9E+01
2.2E+01
Chrysene*
1.4E+02
2.5E+02
1.0E+02
1.3E+02
8.5E+01
1.5E+02
1.9E+02
8.4E+02
7.6E+01
2.4E+01
5.3E+01
Benzo(b)fluoranthene*
9.0E+01
3.8E+02
7.6E+01
9.3E+01
9.1E+01
1.8E+02
1.1E+02
1.1E+03
7.4E+01
2.4E+01
4.1E+01
Benzo(k)fluoranthene*
3.6E+01
1.7E+02
4.5E+01
5.1E+01
3.1E+01
5.9E+01
5.4E+01
6.0E+02
3.7E+01
1.2E+01
2.1E+01
Benzo(e)pyrene
7.2E+01
2.8E+02
5.5E+01
6.9E+01
7.0E+01
1.4E+02
8.2E+01
8.5E+02
6.0E+01
1.8E+01
2.9E+01
Benzo(a)pyrene*
3.0E+01
2.3E+02
4.6E+01
5.3E+01
4.2E+01
6.1E+01
5.2E+01
9.0E+02
4.7E+01
2.2E+01
1.7E+01
Perylene
1.7E+01
7.9E+01
3.0E+01
2.8E+01
1.8E+01
2.9E+01
3.0E+01
2.1E+02
2.2E+01
4.5E+00
1.1E+01
Indeno(1.2.3-cd)pyrene*
6.2E+01
3.0E+02
2.5E+01
6.7E+01
5.4E+01
1.6E+02
6.2E+01
8.2E+02
5.3E+01
2.0E+01
2.8E+01
Dibenz(a,h)antracene*
2.5E+01
1.6E+02
3.6E+01
4.0E+01
2.6E+01
6.5E+01
4.0E+01
4.0E+02
2.6E+01
7.2E+00
1.2E+01
Benzo(g,h,i)perylene*
7.7E+01
3.1E+02
4.9E+01
6.4E+01
6.4E+01
1.6E+02
6.7E+01
5.0E+02
7.2E+01
2.2E+01
3.0E+01
Dibenzo(a,l)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,h)pyrene
BLOQ
2.6E+02
BLOQ
BLOQ
BLOQ
9.2E+01
BLOQ
3.7E+02
BLOQ
BLOQ
BLOQ
Dibenzo(a,i)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,e)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Coronene
5.7E+00
1.0E+02
5.7E+00
5.7E+00
3.4E+01
5.7E+01
5.7E+00
1.9E+02
3.1E+01
5.7E+00
5.7E+00
∑ all 19 PAHs (µg/kg dm)
8.6E+02
3.0E+03
1.5E+03
1.3E+03
6.3E+02
1.3E+03
1.7E+03
8.5E+03
8.7E+02
2.8E+02
4.6E+02
∑12 EPA PAHs (µg/kg dm)
7.7E+02
2.3E+03
1.4E+03
1.2E+03
5.0E+02
1.0E+03
1.5E+03
6.9E+03
7.5E+02
2.5E+02
4.1E+02
TEQPAH (µg/kg dm)
1.3E-01
6.1E-01
1.4E-01
1.7E-01
1.1E-01
2.5E-01
1.8E-01
1.9E+00
1.2E-01
3.9E-02
6.6E-02
Country of origin
PAH (µg/kg dm)
Summaries
Table S1 – C Results of PAHs measurment for sewage sludge compost (Type C)
Location Code
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Type
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
France
Finland
Luxembourg
Spain
Germany
Austria
Austria
Austria
France
France
France
France
France
France
Czech Rep.
United Kingdom
Phenantrene*
2.3E+02
1.0E+02
2.8E+01
3.4E+01
1.4E+02
1.4E+02
5.5E+02
1.5E+02
4.6E+01
2.2E+01
3.2E+01
6.8E+01
6.9E+01
3.1E+02
5.4E+01
1.8E+01
Antracene*
4.9E+01
1.5E+01
8.5E+01
4.6E+00
4.2E+01
2.0E+01
3.9E+01
2.2E+01
9.0E+00
8.2E+00
3.1E+01
1.3E+01
1.4E+01
4.6E+01
2.0E+01
1.8E+01
Fluoranthene*
2.6E+02
2.0E+02
1.0E+03
2.9E+01
3.3E+02
2.4E+02
5.9E+02
4.1E+02
1.1E+02
1.8E+02
3.6E+02
2.2E+02
8.1E+01
3.1E+02
1.8E+02
4.5E+01
Pyrene*
1.6E+02
1.9E+02
8.7E+02
5.6E+01
2.2E+02
1.7E+02
4.2E+02
2.9E+02
8.5E+01
1.2E+02
2.7E+02
1.7E+02
6.7E+01
2.3E+02
1.7E+02
4.5E+01
Benzo(a)antracene*
8.2E+01
5.9E+01
9.3E+02
2.0E+01
8.3E+01
6.3E+01
9.0E+01
8.6E+01
3.0E+01
7.6E+01
9.2E+01
7.2E+01
2.5E+01
9.2E+01
2.0E+02
7.2E+01
Chrysene*
6.5E+01
1.3E+02
1.4E+03
3.7E+01
1.5E+02
9.3E+01
1.3E+02
1.1E+02
4.7E+01
1.2E+02
1.3E+02
1.1E+02
3.4E+01
1.2E+02
3.2E+02
1.8E+02
Benzo(b)fluoranthene*
9.4E+01
1.2E+02
1.3E+03
5.3E+01
1.1E+02
8.0E+01
7.1E+01
1.0E+02
4.4E+01
8.7E+01
1.3E+02
1.0E+02
3.6E+01
9.1E+01
4.1E+02
1.6E+02
Benzo(k)fluoranthene*
2.9E+01
6.6E+01
6.4E+02
2.3E+01
5.3E+01
3.9E+01
3.3E+01
5.6E+01
2.7E+01
4.8E+01
6.7E+01
5.5E+01
2.2E+01
5.4E+01
1.9E+02
7.0E+01
Benzo(e)pyrene
3.2E+01
8.0E+01
9.6E+02
5.7E+01
7.9E+01
5.5E+01
4.4E+01
7.2E+01
3.6E+01
6.7E+01
1.0E+02
7.1E+01
2.5E+01
5.5E+01
3.4E+02
1.4E+02
Benzo(a)pyrene*
7.3E+01
7.0E+01
7.7E+02
4.3E+01
4.9E+01
5.5E+01
3.9E+01
7.0E+01
3.0E+01
5.1E+01
9.4E+01
4.8E+01
2.0E+01
6.3E+01
3.6E+02
8.1E+01
Perylene
9.3E+00
3.5E+01
2.5E+02
3.1E+00
3.3E+01
2.4E+01
9.7E+00
3.5E+01
2.6E+01
2.0E+01
2.8E+01
2.6E+01
3.1E+00
1.2E+01
1.3E+02
3.0E+01
Indeno(1,2,3-cd)pyrene*
3.4E+01
9.5E+01
7.2E+02
2.5E+01
7.3E+01
7.5E+01
3.5E+01
6.6E+01
4.3E+01
5.0E+01
8.7E+01
1.0E+02
4.1E+01
8.7E+01
3.4E+02
9.0E+01
Dibenz(a,h)antracene*
2.0E+01
3.3E+01
4.1E+02
3.2E+00
4.4E+01
3.1E+01
1.7E+01
2.9E+01
2.3E+01
2.8E+01
3.7E+01
3.2E+00
3.2E+00
4.5E+01
1.5E+02
4.9E+01
Benzo(g,h,i)perylene*
4.3E+01
9.0E+01
8.7E+02
6.7E+01
8.6E+01
8.6E+01
5.5E+01
9.1E+01
5.4E+01
6.0E+01
8.2E+01
9.6E+01
2.7E+01
8.1E+01
4.1E+02
1.2E+02
Dibenzo(a,l)pyrene
BLOQ
BLOQ
7.1E+01
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
8.6E+00
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,h)pyrene
BLOQ
3.4E+01
4.3E+02
BLOQ
BLOQ
BLOQ
BLOQ
3.7E+01
BLOQ
BLOQ
4.8E+01
BLOQ
BLOQ
BLOQ
3.5E+02
3.5E+01
Dibenzo(a,i)pyrene
BLOQ
BLOQ
2.8E+01
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,e)pyrene
BLOQ
BLOQ
7.6E+01
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Coronene
5.7E+00
4.3E+01
3.6E+02
5.7E+00
5.7E+00
5.7E+00
4.7E+01
5.0E+01
5.7E+00
5.7E+00
4.4E+01
5.7E+00
5.7E+00
1.5E+01
1.8E+02
5.0E+01
∑ all 19 PAHs (µg/kg dm)
1.2E+03
1.4E+03
1.1E+04
4.6E+02
1.5E+03
1.2E+03
2.2E+03
1.7E+03
6.1E+02
9.4E+02
1.6E+03
1.2E+03
4.7E+02
1.6E+03
3.8E+03
1.2E+03
∑12 EPA PAHs (µg/kg dm)
1.1E+03
1.2E+03
9.1E+03
3.9E+02
1.4E+03
1.1E+03
2.1E+03
1.5E+03
5.4E+02
8.5E+02
1.4E+03
1.1E+03
4.4E+02
1.5E+03
2.8E+03
9.4E+02
TEQPAH (µg/kg dm)
9.9E-02
2.0E-01
2.0E+00
5.8E-02
1.8E-01
1.4E-01
1.0E-01
1.7E-01
9.2E-02
1.5E-01
2.1E-01
1.4E-01
5.9E-02
1.9E-01
6.7E-01
2.3E-01
Country of origin
PAH (µg/kg dm)
Summaries
Table S1-D Results of PAHs measurement for mechanical biological treatment compost (Type D)
Location Code
1
2
3
4
5
6
7
8
Type
D
D
D
D
D
D
D
D
France
France
France
France
France
Portugal
Portugal
Phenantrene*
1.2E+02
1.7E+02
2.2E+02
9.6E+01
9.1E+01
9.8E+01
4.9E+01
2.2E+02
Antracene*
5.7E+00
4.6E+00
2.4E+01
1.0E+01
9.6E+00
5.2E+00
3.5E+00
3.3E+01
Fluoranthene*
9.1E+01
8.5E+01
3.0E+02
1.1E+02
9.6E+01
6.5E+01
3.4E+01
3.2E+02
Pyrene*
6.4E+01
8.7E+01
1.9E+02
9.6E+01
7.7E+01
6.6E+01
4.2E+01
2.3E+02
Benzo(a)antracene*
3.0E+01
2.4E+01
1.0E+01
4.1E+01
4.7E+01
2.0E+01
2.5E+01
1.7E+02
Chrysene*
4.0E+01
4.9E+01
1.5E+02
6.1E+01
6.1E+01
3.8E+01
3.3E+01
2.1E+02
Benzo(b)fluoranthene*
4.6E+01
3.4E+01
1.1E+02
5.0E+01
5.2E+01
2.7E+01
2.3E+01
1.7E+02
Benzo(k)fluoranthene*
3.0E+01
1.4E+01
5.6E+01
2.9E+01
3.3E+01
1.5E+01
1.3E+01
8.9E+01
Benzo(e)pyrene
3.6E+01
8.4E+01
8.5E+01
4.3E+01
4.7E+01
2.5E+01
2.0E+01
1.4E+02
Benzo(a)pyrene*
3.3E+01
2.5E+01
6.2E+01
3.5E+01
4.6E+01
1.8E+01
2.3E+01
1.4E+02
Perylene
1.9E+01
2.0E+01
3.2E+01
2.2E+01
2.8E+01
1.4E+01
5.8E+00
5.6E+01
Indeno(1,2,3-cd)pyrene*
6.4E+01
2.3E+01
6.2E+01
3.9E+01
4.0E+01
2.4E+01
1.9E+01
1.3E+02
Dibenz(a,h)antracene*
3.2E+00
2.0E+01
3.2E+00
2.2E+01
2.3E+01
1.2E+01
1.6E+01
5.9E+01
Benzo(g,h,i)perylene*
4.6E+01
3.3E+01
7.1E+01
5.1E+01
4.2E+01
3.0E+01
4.0E+01
1.8E+02
Dibenzo(a,l)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,h)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,i)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,e)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Coronene
5.7E+00
5.7E+00
5.7E+00
2.2E+01
5.7E+00
5.7E+00
3.2E+01
5.7E+00
∑ all 19 PAHs (µg/kg dm)
6.3E+02
6.8E+02
1.4E+03
7.2E+02
7.0E+02
4.6E+02
3.8E+02
2.2E+03
∑12 EPA PAHs (µg/kg dm)
5.7E+02
5.7E+02
1.3E+03
6.4E+02
6.2E+02
4.2E+02
3.2E+02
2.0E+03
TEQPAH (µg/kg dm)
8.1E-02
6.2E-02
1.4E-01
9.7E-02
1.1E-01
5.2E-02
5.2E-02
3.0E-01
Country of origin
PAH (µg/kg dm)
Summaries
UK
Table S1 – part E – Results of PAHs measurement for manure and biowaste digestate (Type F), manure and energy crop digestate (Type G), MBT digestate (Type H) and other compost
samples (Type i)
Location Code
1
2
3
4
5
1
1
2
1
2
3
4
5
Type
F
F
F
F
F
G
H
H
i
i
i
i
i
Belgium
Luxembourg
Austria
Belgium
Belgium
Austria
Netherland
France
France
Netherland
Austria
Austria
France
Phenantrene*
5.5E+01
4.9E+01
2.7E+01
2.4E+02
2.7E+02
6.9E+01
2.2E+01
9.3E+01
3.3E+01
3.9E+03
5.3E+01
7.0E+01
9.6E+01
Antracene*
4.6E+00
4.6E+00
4.6E+00
3.8E+01
3.3E+01
1.1E+01
1.7E+01
1.9E+01
9.5E+00
3.5E+02
2.5E+01
2.0E+01
1.0E+01
Fluoranthene*
2.5E+01
1.4E+02
1.7E+01
1.7E+02
2.0E+02
1.2E+02
1.3E+02
2.8E+02
5.0E+01
4.8E+03
6.3E+01
4.5E+02
1.5E+02
Pyrene*
3.1E+01
1.1E+02
1.9E+01
1.1E+02
1.5E+02
1.0E+02
1.1E+02
1.7E+02
2.2E+01
3.2E+03
5.4E+01
4.7E+02
1.1E+02
Benzo(a)antracene*
2.5E+01
6.2E+01
5.7E+00
6.4E+01
5.8E+01
4.5E+01
9.0E+01
9.5E+01
2.0E+01
1.9E+03
3.4E+01
1.3E+02
6.8E+01
Chrysene*
2.7E+01
9.0E+01
1.0E+01
6.6E+01
7.2E+01
6.8E+01
1.5E+02
1.4E+02
6.6E+01
2.1E+03
4.5E+01
1.7E+02
9.5E+01
Benzo(b)fluoranthene*
6.3E+01
8.6E+01
9.9E+00
1.5E+02
7.5E+01
6.1E+01
1.9E+02
1.1E+02
9.2E+01
1.6E+03
6.6E+01
8.7E+01
9.1E+01
Benzo(k)fluoranthene*
2.1E+01
4.7E+01
2.4E+00
6.1E+01
4.6E+01
4.3E+01
8.8E+01
5.3E+01
3.5E+01
8.5E+02
3.3E+01
4.1E+01
5.0E+01
Benzo(e)pyrene
2.4E+01
6.4E+01
3.4E+00
7.6E+01
1.1E+02
3.9E+01
1.4E+02
8.3E+01
6.8E+01
1.5E+03
6.5E+01
7.1E+01
8.6E+01
Benzo(a)pyrene*
2.6E+01
8.3E+01
2.8E+00
1.8E+02
1.4E+02
4.5E+01
1.5E+02
7.3E+01
5.2E+01
1.4E+03
6.4E+01
5.3E+01
8.9E+01
Perylene
3.1E+00
3.0E+01
3.1E+00
4.1E+01
8.7E+00
1.8E+01
5.7E+01
2.9E+01
2.8E+01
3.9E+02
2.4E+01
3.1E+01
3.1E+01
Indeno(1,2,3-cd)pyrene*
2.7E+01
8.0E+01
3.0E+00
3.0E+00
3.0E+00
3.3E+01
1.5E+02
6.9E+01
7.0E+01
9.1E+02
8.3E+01
4.5E+01
7.2E+01
Dibenz(a,h)antracene*
1.4E+01
BLOQ
3.2E+00
3.2E+00
3.2E+00
2.7E+01
6.8E+01
3.9E+01
2.4E+01
5.8E+02
3.0E+01
3.2E+01
4.0E+01
Benzo(g,h,i)perylene*
Country of origin
PAH (µg/kg dm)
Summaries
4.0E+01
8.6E+01
3.4E+00
3.4E+00
3.4E+00
6.0E+01
1.7E+02
7.5E+01
7.4E+01
1.3E+03
8.2E+01
8.1E+01
8.5E+01
Dibenzo(a,l)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
1.2E+02
1.2E+01
BLOQ
1.2E+01
Dibenzo(a,h)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
7.7E+01
BLOQ
BLOQ
6.5E+02
5.1E+01
1.8E+01
4.9E+01
Dibenzo(a,i)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
Dibenzo(a,e)pyrene
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
BLOQ
2.1E+02
BLOQ
BLOQ
BLOQ
Coronene
5.7E+00
5.7E+00
5.7E+00
5.7E+00
5.7E+00
5.7E+00
4.0E+01
4.0E+01
2.8E+01
5.0E+02
8.7E+01
7.9E+01
4.3E+01
∑ all 19 PAHs (µg/kg dm)
3.9E+02
9.3E+02
1.2E+02
1.2E+03
1.2E+03
7.4E+02
1.6E+03
1.4E+03
6.7E+02
2.6E+04
8.7E+02
1.8E+03
1.2E+03
∑12 EPA PAHs (µg/kg dm)
3.6E+02
8.3E+02
1.1E+02
1.1E+03
1.0E+03
6.8E+02
1.3E+03
1.2E+03
5.5E+02
2.3E+04
6.3E+02
1.6E+03
9.6E+02
TEQPAH (µg/kg dm)
6.6E-02
1.2E-01
1.0E-02
1.3E-01
1.0E-01
1.2E-01
3.0E-01
1.8E-01
1.2E-01
2.8E+00
1.3E-01
1.5E-01
1.7E-01
In italic bold are indicated values as LOD/2, BLOQ-below limit of quantification, PAHs – polycyclic aromatic hydrocarbons, *-12 EPA PAHs, TEQPAH – toxic equivalent of 2,3,7,8 TCDD for
PAHs calculated from analytical results and induction equivalency factors for PAHs
Table S1-part F – Recoveries and limits of quantification of studied PAHs
PAH
LOQ µg/kg
Recovery (%)
Phenanthrene
10.7
62
Anthracene
7.8
64
Fluoranthene
5.3
67
Pyrene
6.0
68
Benzo(a)anthracene
5.6
74
Chrysene
6.8
74
Benzo(b)fluoranthene
10.7
75
Benzo(k)fluoranthene
11.6
75
Benzo(e)pyrene
11.5
70
Benzo(a)pyrene
6.4
76
Perilene
7.4
69
Indeno(1,2,3-cd)pyrene
13.6
67
Dibenzo(a,h)anthracene
7.9
74
Benzo(g,h,i)perilene
11.6
56
Dibenzo(a,l)pyrene
92.9
63
Dibenzo(a,h)pyrene
97.0
63
Dibenzo(a,i)pyrene
848.0
63
Dibenzo(a,e)pyrene
961.9
63
Coronene
88.1
31
Table S2-A : 17 EPA PCDDs/Fs values for 17 selected samples
Sample number
1
2
3
4
1
2
1
2
3
1
2
1
2
1
1
2
1
Sample type
A
A
A
A
B
B
C
C
C
D
D
F
F
G
H
H
i
Country of origin
Belgium
Germany
Belgium
Belgium
Belgium
Germany
Luxembourg
Germany
France
France
United Kingdom
Luxembourg
Belgium
Austria
Netherland
France
Netherland
PCDDs/Fs
2378-TCDF
2.1E+00
<1.1E+00
1.6E+00
9.1E-01
1.8E+00
1.4E+00
<5.9E+00
2.3E+00
<1.7E+00
7.9E-01
1.6E+00
<7.7E-01
<8.4E-01
<6.1E-01
1.1E+00
1.1E+00
3.2E+00
ng/kg dm
12378-PeCDF
1.0E+00
<7.4E-01
<1.1E+00
<1.3E+00
<9.9E-01
1.6E+00
<2.6E+00
<1.8E+00
<1.6E+00
<7.0E-01
<9.0E-01
<4.5E-01
<7.3E-01
<8.0E-01
7.6E-01
<8.6E-01
1.9E+00
23478-PeCDF
1.6E+00
1.0E+00
1.2E+00
<1.3E+00
1.1E+00
1.9E+00
<2.3E+00
<1.8E+00
<1.6E+00
<8.2E-01
<1.8E+00
<5.5E-01
<7.2E-01
<8.3E-01
9.0E-01
<8.1E-01
<2.6E+00
123478-HxCDF
1.1E+00
1.1E+00
<1.2E+00
<1.4E+00
8.3E-01
5.3E+00
<5.0E+00
<3.7E+00
<1.9E+00
<1.3E+00
1.4E+00
<5.1E+00
<1.8E+01
<1.8E+01
<7.1E-01
<2.4E+00
<7.3E+00
123678-HxCDF
1.0E+00
1.7E+00
<1.2E+00
<1.4E+00
8.1E-01
5.8E+00
<4.9E+00
<3.6E+00
<1.8E+00
<1.3E+00
1.9E+00
<8.0E+00
<1.8E+01
<1.7E+01
7.7E-01
<2.3E+00
<6.1E+00
234678-HxCDF
<9.7E-01
<9.6E-01
<1.2E+00
<1.5E+00
<8.5E-01
5.2E+00
<4.9E+00
<3.8E+00
<1.9E+00
<1.3E+00
<1.5E+00
<5.9E+00
<2.3E+01
<2.5E+01
<7.6E-01
<2.5E+00
<8.1E+00
123789-HxCDF
<1.2E+00
<1.2E+00
<1.6E+00
<1.7E+00
<1.0E+00
1.1E+00
<5.1E+00
<4.6E+00
<2.3E+00
<1.7E+00
<2.4E+00
<8.1E+00
<2.3E+01
<3.6E+01
<9.5E-01
<2.9E+00
<1.2E+01
1234678-HpCDF
7.0E+00
3.7E+00
5.3E+00
2.2E+00
3.5E+00
4.0E+01
<3.3E+00
4.6E+00
2.5E+00
3.6E+00
9.7E+00
<3.4E+00
<4.5E+00
<1.1E+01
3.7E+00
<2.6E+00
3.6E+01
1234789-HpCDF
<1.9E+00
<1.2E+00
<1.8E+00
<1.8E+00
<1.9E+00
3.9E+00
<3.7E+00
<3.1E+00
<2.6E+00
<2.2E+00
<3.7E+00
<2.9E+00
<3.3E+00
<4.8E+00
<1.9E+00
<3.4E+00
1.2E+01
OCDF
4.9E+00
5.3E+00
5.7E+00
2.9E+00
6.1E+00
3.9E+01
2.5E+00
6.6E+00
5.6E+00
7.5E+00
1.5E+01
<1.6E+00
<2.3E+00
<1.7E+00
4.9E+00
2.9E+00
1.5E+01
2378-TCDD
<9.9E-01
<9.9E-01
<9.3E-01
<1.3E+00
<1.1E+00
<8.2E-01
<5.3E+00
<1.7E+00
<1.4E+00
<9.8E-01
<1.6E+00
<9.5E+00
<9.0E-01
<7.0E-01
<7.1E-01
<1.2E+00
<1.9E+00
12378-PeCDD
<9.7E-01
<1.0E+00
<1.3E+00
<1.5E+00
<1.3E+00
<1.1E+00
<3.3E+00
<2.1E+00
<2.2E+00
<1.2E+00
<1.2E+00
<1.9E+00
<1.7E+00
<1.5E+00
<1.1E+00
<1.3E+00
<3.8E+00
123478-HxCDD
<7.4E-01
<9.1E-01
<1.5E+00
<1.8E+00
<1.2E+00
<6.6E-01
<3.9E+00
<2.8E+00
<2.4E+00
2.3E+00
<1.6E+00
<2.2E+00
<4.9E+00
<1.1E+01
<1.0E+00
<1.5E+00
<4.9E+00
123678-HxCDD
1.6E+00
<9.3E-01
<1.5E+00
<1.8E+00
<1.3E+00
<6.6E-01
<3.8E+00
<2.8E+00
4.1E+00
<1.2E+00
<1.9E+00
<2.2E+00
<4.8E+00
<9.1E+00
<9.8E-01
<1.5E+00
<5.4E+00
123789-HxCDD
<1.3E-02
<1.3E-02
<1.4E+00
<1.0E-02
<1.0E-02
<6.3E-01
<3.7E+00
<2.6E+00
<1.3E-02
2.1E+00
<1.0E-02
<2.1E+00
<4.6E+00
<9.9E+00
<9.4E-01
<1.0E-02
<4.6E+00
1234678-HpCDD
7.1E+01
1.7E+01
3.2E+01
4.3E+01
1.6E+01
1.4E+01
8.7E+00
2.2E+01
9.9E+01
2.3E+01
4.7E+01
1.8E+00
3.8E+00
<4.2E+00
1.0E+01
5.9E+01
1.1E+02
OCDD
3.2E+02
6.7E+01
1.8E+02
1.7E+02
9.7E+01
5.3E+01
2.8E+01
8.6E+01
2.3E+02
1.9E+02
3.9E+02
7.3E+00
1.1E+01
7.9E+00
5.5E+01
2.1E+02
3.6E+02
Total 17 EPA PCDDs/Fs
4.1E+02
9.7E+01
2.3E+02
2.2E+02
1.3E+02
1.7E+02
4.0E+01
1.2E+02
3.4E+02
2.3E+02
4.7E+02
9.2E+00
1.5E+01
7.9E+00
7.7E+01
2.7E+02
5.4E+02
Total-TEQ LB WHO98
2.3E+00
1.0E+00
1.1E+00
5.6E-01
1.1E+00
3.4E+00
9.0E-02
5.1E-01
2.2E+00
8.1E-01
1.1E+00
3.0E-02
4.0E-02
0.0E+00
8.1E-01
1.3E+00
2.0E+00
Total-TEQ UB WHO98
4.5E+00
3.6E+00
4.4E+00
5.1E+00
3.9E+00
5.6E+00
1.4E+01
7.8E+00
7.9E+00
4.2E+00
5.7E+00
1.5E+01
1.3E+01
1.5E+01
3.2E+00
5.6E+00
1.4E+01
Total-TEQ LB WHO2006
2.0E+00
8.3E-01
9.4E-01
5.9E-01
8.9E-01
3.0E+00
1.0E-01
5.3E-01
2.2E+00
8.5E-01
1.2E+00
3.0E-02
4.0E-02
0.0E+00
6.3E-01
1.4E+00
2.1E+00
Total-TEQ UB WHO2006
4.3E+00
3.4E+00
4.2E+00
4.8E+00
3.7E+00
5.2E+00
1.3E+01
7.4E+00
7.6E+00
4.0E+00
5.4E+00
1.5E+01
1.3E+01
1.5E+01
3.0E+00
5.5E+00
1.3E+01
Total I-TEQ LB
2.6E+00
1.1E+00
1.3E+00
7.1E-01
1.2E+00
3.5E+00
1.2E-01
5.9E-01
1.7E+00
9.9E-01
1.5E+00
3.0E-02
5.0E-02
1.0E-02
8.6E-01
9.1E-01
2.4E+00
Total I-TEQ UB
4.3E+00
3.1E+00
3.9E+00
4.5E+00
3.4E+00
5.1E+00
1.2E+01
6.8E+00
6.3E+00
3.7E+00
5.4E+00
1.4E+01
1.2E+01
1.5E+01
2.7E+00
4.5E+00
1.2E+01
Total TEQH4IIELB
5.8E+00
1.7E+00
2.8E+00
2.4E+00
2.1E+00
5.8E+00
4.3E-01
2.0E+00
5.3E+00
2.4E+00
3.5E+00
8.8E-02
1.8E-01
3.9E-03
1.6E+00
3.2E+00
8.3E+00
Total TEQH4IIE UB
7.9E+00
4.5E+00
6.1E+00
7.0E+00
5.0E+00
7.7E+00
1.6E+01
9.4E+00
1.1E+01
5.5E+00
8.3E+00
1.5E+01
1.5E+01
1.9E+01
3.8E+00
7.7E+00
2.0E+01
Table S2-B – Recoveries and limits of quantification of studied PCDDs/Fs
PCDDs/Fs
%
ng/kg
recovery min
recovery max
recovery average
LOQ min
LOQ max
LOQ average
2378-TCDF
57
74
68
0.6
5.9
1.2
12378-PeCDF
61
146
78
0.5
2.6
1.1
23478-PeCDF
44
118
76
0.6
2.6
1.1
123478-HxCDF
30
102
79
0.7
17.9
3.7
123678-HxCDF
32
93
69
0.7
18.1
3.7
234678-HxCDF
27
102
77
0.8
24.6
4.4
123789-HxCDF
23
109
77
1.0
36.1
5.6
1234678-HpCDF
17
117
72
0.9
12.4
3.0
1234789-HpCDF
25
136
73
1.2
10.0
2.9
OCDF
65
185
87
1.2
3.7
2.0
2378-TCDD
7
66
58
0.7
9.5
1.8
12378-PeCDD
63
107
76
1.0
3.8
1.7
123478-HxCDD
20
109
80
0.7
10.5
2.4
123678-HxCDD
30
106
72
0.7
9.1
2.4
123789-HxCDD
25
121
75
0.6
9.9
2.9
1234678-HpCDD
20
136
78
1.1
4.2
1.8
OCDD
65
203
93
1.2
3.7
2.2
Table S3-A– Dioxin-like PCBs values for 17 selected samples
Number of sample
1
2
3
4
1
2
1
2
3
1
2
1
2
1
1
2
1
Sample code
A
A
A
A
B
B
C
C
C
D
D
F
F
G
H
H
i
Country of origin
Belgium
Germany
Belgium
Belgium
Belgium
Germany
Luxembourg
Germany
France
France
UK
Luxembourg
Belgium
Austria
Netherland
France
Netherland
Dl PCBs
PCB77
5.7E+01
3.4E+01
9.7E+01
6.3E+01
5.3E+01
3.8E+01
1.0E+02
7.9E+01
1.4E+02
5.9E+01
1.5E+02
6.0E+00
3.4E+01
1.3E+01
2.3E+01
2.1E+02
3.4E+02
ng/kg, dm
PCB81
3.8E+00
3.0E+00
8.6E+00
7.0E+00
3.9E+00
4.2E+00
2.3E+01
4.7E+00
1.2E+01
3.9E+00
8.1E+00
<6.0E-01
2.2E+00
<2.1E+00
1.4E+00
1.4E+01
2.2E+01
PCB126
1.1E+01
7.9E+00
1.4E+01
8.7E+00
9.5E+00
1.0E+01
<7.0E+02
2.3E+01
1.6E+01
6.5E+00
3.4E+00
<6.0E-01
4.5E+00
<2.0E+00
2.7E+00
9.9E+00
1.2E+01
PCB169
1.4E+00
<1.2E+00
<1.6E+00
<1.9E+00
<1.5E+00
2.3E+00
<3.2E+00
3.2E+00
<2.2E+00
<1.3E+00
<1.9E+00
<1.3E+00
<2.2E+00
<2.7E+00
<8.0E-01
<2.0E+00
<5.1E+00
PCB105
5.0E+02
1.9E+02
6.1E+02
5.3E+02
4.0E+02
1.7E+02
3.1E+02
4.0E+02
1.0E+03
1.0E+03
3.5E+02
2.1E+01
2.1E+02
8.0E+01
1.5E+02
1.9E+03
1.4E+03
PCB114
2.7E+01
1.2E+01
3.3E+01
3.1E+01
2.0E+01
1.1E+01
8.2E+02
2.2E+01
4.8E+01
5.6E+01
2.3E+01
1.7E+00
1.2E+01
5.0E+00
8.8E+00
9.5E+01
1.0E+02
PCB118
1.6E+03
8.4E+02
2.1E+03
2.1E+03
1.3E+03
7.5E+02
1.4E+02
1.7E+03
3.4E+03
2.8E+03
1.1E+03
6.0E+01
8.8E+02
8.1E+01
6.8E+02
4.4E+03
4.0E+02
PCB123
2.5E+02
1.8E+02
3.5E+02
5.0E+02
1.9E+02
1.6E+02
1.6E+02
4.0E+02
4.1E+02
3.2E+02
1.5E+02
8.3E+00
1.4E+02
8.1E+01
1.2E+02
4.9E+02
5.5E+02
PCB156
4.9E+02
3.8E+02
5.4E+02
1.0E+03
4.2E+02
3.3E+02
2.5E+02
7.3E+02
6.7E+02
4.4E+02
2.6E+02
8.9E+00
2.3E+02
1.6E+02
2.6E+02
7.0E+02
7.5E+02
PCB157
6.0E+01
4.0E+01
6.8E+01
9.9E+01
5.2E+01
3.7E+01
3.9E+01
8.0E+01
1.2E+02
7.7E+01
3.0E+01
1.6E+00
2.6E+01
1.3E+01
2.6E+01
1.2E+02
1.1E+02
PCB167
2.3E+02
1.8E+02
2.6E+02
4.3E+02
1.9E+02
1.7E+02
1.0E+02
3.7E+02
2.8E+02
1.9E+02
1.2E+02
3.9E+00
1.1E+02
8.4E+01
1.3E+02
2.8E+02
2.7E+02
PCB189
5.1E+01
5.0E+01
5.2E+01
1.8E+02
5.1E+01
5.7E+01
3.4E+01
1.0E+02
5.0E+01
2.2E+01
2.0E+01
1.1E+00
2.2E+01
1.1E+01
2.7E+01
5.0E+01
6.7E+01
Total dl-PCBs
3.3E+03
1.9E+03
4.2E+03
5.0E+03
2.7E+03
1.7E+03
2.0E+03
4.0E+03
6.1E+03
5.0E+03
2.2E+03
1.1E+02
1.7E+03
5.3E+02
1.4E+03
8.3E+03
4.1E+03
Total-TEQ LB WHO98
1.7E+00
1.1E+00
2.1E+00
1.8E+00
1.4E+00
1.4E+00
6.4E-01
3.0E+00
2.5E+00
1.4E+00
6.8E-01
1.0E-02
7.1E-01
1.1E-01
5.3E-01
2.2E+00
1.9E+00
Total-TEQ UB WHO98
1.7E+00
1.2E+00
2.1E+00
1.8E+00
1.4E+00
1.4E+00
7.0E+01
3.0E+00
2.5E+00
1.4E+00
7.0E-01
9.0E-02
7.4E-01
3.5E-01
5.3E-01
2.2E+00
2.0E+00
Total-TEQ LB WHO2006
1.3E+00
8.5E-01
1.6E+00
1.0E+00
1.0E+00
1.2E+00
8.0E-02
2.5E+00
1.8E+00
8.0E-01
4.3E-01
0.0E+00
5.0E-01
1.0E-02
3.3E-01
1.3E+00
1.3E+00
Total-TEQ UB WHO2006
1.3E+00
8.9E-01
1.6E+00
1.1E+00
1.1E+00
1.2E+00
7.0E+01
2.5E+00
1.8E+00
8.4E-01
4.8E-01
1.0E-01
5.8E-01
3.0E-01
3.5E-01
1.3E+00
1.5E+00
Total TEQH4IIE LB
1.1E+00
8.1E-01
1.5E+00
9.3E-01
9.8E-01
1.1E+00
9.2E-02
2.4E+00
1.7E+00
6.8E-01
3.9E-01
9.4E-04
4.7E-01
5.9E-03
2.9E-01
1.1E+00
1.3E+00
Total TEQH4IIE UB
1.1E+00
8.1E-01
1.5E+00
9.3E-01
9.8E-01
1.1E+00
7.0E+01
2.4E+00
1.7E+00
6.8E-01
3.9E-01
6.3E-02
4.7E-01
2.1E-01
2.9E-01
1.1E+00
1.3E+00
Legend: PCB-polychlorinated biphenyl, TEQ – toxic equivalent of 2,3,7,8-tetrachlorodibenzo-p-dioxin, LB-lower bound value, UB-upper bound value, TEQH4IIE-toxic equivalent of 2,3,7,8
TCDD calculated from analytical results and relative potencies (REPs) of PCDDs/Fs or DL-PCBs
Table S3-B Recoveries and limits of quantification (LOQ) for dioxin-like PCBs
dlPCBs
)
%
ng/kg
recovery min
recovery max
recovery average
LOQ
min
LOQ
max
LOQ
average
PCB77
2
81
67
0.5
22.0
3.3
PCB81
3
82
69
0.6
20.2
3.1
PCB126
60
77
69
0.6
697.2
36.7
PCB169
47
81
67
0.8
5.1
2.0
PCB105
62
136
78
0.5
14.3
1.9
PCB114
58
135
73
0.5
20.7
2.2
PCB118
59
137
72
0.4
21.9
2.2
PCB123
59
143
73
0.4
24.0
2.3
PCB156
65
148
79
0.7
7.5
2.4
PCB157
62
137
77
0.6
6.2
2.4
PCB167
23
149
77
0.7
12.8
3.0
PCB189
37
63
54
0.7
3.6
1.7
Table S4: Results of 6 indicator PCBs and OCPs for 17 selected samples
Nr of sample
1
2
3
4
1
2
1
2
3
1
2
1
2
1
1
2
1
Sample code
A
A
A
A
B
B
C
C
C
D
D
F
F
G
H
H
i
Country of origin
Belgium
Germany
Belgium
Belgium
Belgium
Germany
Luxembourg
Germany
France
France
United Kingdom
Luxembourg
Belgium
Austria
Netherland
France
Netherland
Cl-mix
PCB 28
6.1E-01
4.1E-01
1.1E+00
8.3E-01
6.6E-01
3.2E-01
1.0E+00
8.9E-01
9.8E-01
5.6E-01
2.1E+00
3.0E-01
8.5E-01
6.2E-01
2.1E-01
2.9E+00
5.3E+00
µg/kg
PCB 52
8.2E-01
5.1E-01
1.0E+00
1.2E+00
6.1E-01
4.5E-01
7.6E-01
9.5E-01
1.9E+00
1.3E+00
1.2E+00
1.6E-01
6.4E-01
4.2E-01
2.9E-01
3.4E+00
4.2E+00
dm
PCB 101
3.1E+00
2.4E+00
4.1E+00
5.6E+00
2.2E+00
1.9E+00
1.1E+00
4.1E+00
4.6E+00
4.5E+00
1.9E+00
1.6E-01
1.5E+00
1.2E+00
1.3E+00
5.2E+00
4.2E+00
PCB 153
6.7E+00
5.7E+00
8.8E+00
1.4E+01
5.3E+00
4.6E+00
2.7E+00
1.1E+01
8.6E+00
6.3E+00
3.6E+00
1.4E-01
3.6E+00
2.7E+00
3.4E+00
7.1E+00
6.2E+00
PCB 138
6.2E+00
5.2E+00
7.4E+00
1.1E+01
5.0E+00
4.1E+00
2.4E+00
9.3E+00
7.6E+00
5.9E+00
3.2E+00
1.3E-01
2.8E+00
2.3E+00
2.9E+00
7.2E+00
6.0E+00
PCB 180
4.2E+00
3.9E+00
4.8E+00
1.2E+01
4.2E+00
3.5E+00
2.4E+00
7.7E+00
4.8E+00
2.3E+00
2.3E+00
9.9E-02
2.0E+00
1.2E+00
2.0E+00
4.0E+00
4.1E+00
PeCB
9.1E-02
6.2E-02
3.3E-01
3.9E-02
1.8E-01
8.1E-02
8.8E-02
8.1E-02
9.2E-02
5.9E-02
6.7E-02
4.9E-02
2.8E-01
1.0E-01
1.9E-01
7.6E-02
3.4E-01
HCB
3.2E-01
6.4E-01
1.1E+00
1.6E-01
4.0E-01
3.6E-01
3.9E-01
4.6E-01
2.5E-01
1.5E-01
4.7E-01
6.9E-02
3.6E-01
1.5E-01
1.5E+00
1.9E-01
5.9E+00
a-HCH
1.6E-01
1.9E-01
1.3E-01
1.6E-01
1.7E-01
1.6E-01
4.2E+00
1.6E-01
1.5E-01
5.6E-01
2.2E-01
1.1E+00
1.3E-01
1.5E-01
1.2E-01
1.5E-01
8.9E-01
b-HCH
4.5E-02
1.2E-01
2.5E-02
3.9E-02
1.5E-01
3.2E-02
1.8E-01
2.7E-02
1.2E-01
5.9E-01
1.2E-01
4.9E-02
-
2.5E-02
2.6E-02
7.6E-02
5.5E-01
Lindane
3.0E-01
3.5E-01
3.0E-01
2.4E-01
5.0E-01
2.6E-01
5.2E+00
3.0E-01
2.8E-01
4.3E+00
3.6E+00
1.6E+00
2.0E-01
2.8E-01
2.0E-01
3.0E-01
4.9E-01
d-HCH
9.1E-02
1.2E-01
1.0E-01
1.2E-01
1.1E-01
1.1E-01
1.3E+00
1.1E-01
9.2E-02
3.6E-01
1.5E-01
6.9E-01
8.7E-02
1.4E-01
9.2E-02
7.6E-02
3.4E-01
o.p'-DDE
1.2E+00
4.1E-02
2.5E-01
1.2E-01
1.8E-01
4.9E-02
1.1E-01
1.1E-01
1.8E-01
4.2E-01
1.0E-01
3.0E-02
1.0E-01
3.8E-02
2.6E-02
2.3E-01
1.2E-01
p.p'-DDE
4.4E+01
1.3E+00
1.4E+01
3.5E+00
9.5E+00
1.2E+00
5.6E+00
3.6E+00
8.5E+00
2.8E+00
2.7E+00
1.0E+00
1.3E+00
3.1E-01
1.0E+00
5.9E+00
1.4E+00
o.p'-DDD
3.2E+00
1.4E-01
3.3E-01
3.6E-01
1.8E-01
1.9E-01
6.7E+00
1.9E+00
3.1E-01
5.6E-01
5.4E-01
3.0E-02
1.5E-02
1.3E-02
1.3E-01
5.7E-01
9.2E-01
p.p'-DDD
5.7E+00
4.9E-01
1.5E+00
7.5E-01
8.8E-01
3.6E-01
5.9E-01
4.9E-01
3.7E-01
3.0E+00
2.6E+00
6.9E-02
7.3E-02
2.5E-02
4.9E-01
1.9E+00
3.6E+00
o.p'-DDT
3.0E-01
6.2E-02
7.6E-02
1.2E-01
2.8E-01
6.5E-02
1.6E-01
2.7E-02
9.2E-02
3.3E-01
1.5E-01
4.9E-02
2.9E-02
3.8E-02
6.6E-02
1.9E-01
1.8E-01
p.p'DDT
1.1E+00
1.9E-01
1.3E-01
3.6E-01
1.4E+00
1.9E-01
4.6E-01
1.6E-01
2.5E-01
1.8E+00
6.7E-01
1.1E-01
2.9E-02
6.3E-02
1.7E-01
6.8E-01
5.8E-01
e-HCH
4.5E-02
4.1E-02
-
3.9E-02
-
-
2.5E-01
5.4E-02
3.1E-02
8.9E-02
6.7E-02
8.9E-02
4.4E-02
1.3E-02
-
3.8E-02
9.2E-02
SUMA PCBs
2.2E+01
1.8E+01
2.7E+01
4.4E+01
1.8E+01
1.5E+01
1.0E+01
3.4E+01
2.9E+01
2.1E+01
1.4E+01
9.8E-01
1.1E+01
8.5E+00
1.0E+01
3.0E+01
3.0E+01
SUMA HCHs
5.9E-01
7.8E-01
5.6E-01
5.5E-01
9.2E-01
5.7E-01
1.1E+01
6.0E-01
6.4E-01
5.8E+00
4.1E+00
3.4E+00
4.2E-01
5.9E-01
4.4E-01
6.1E-01
2.3E+00
SUMA DDTs
5.6E+01
2.2E+00
1.7E+01
5.2E+00
1.2E+01
2.1E+00
1.4E+01
6.3E+00
9.7E+00
8.9E+00
6.8E+00
1.3E+00
1.6E+00
4.9E-01
1.9E+00
9.4E+00
6.8E+00
Legend: OCP-organochlorine pesticides, PCB- polychlorinated biphenyl, PeCB – pentachlorobenzene, HCH-hexachlorocyclohexane, DDE-dichlorodiphenyldichloroethylene, DDTdichlorodiphenyltrichloroethane, HCB-hexachlorobenzene
Table S5: Results of H4IIE-luc bioassay (TEQbio) and TEQPAHs for 88 tested samples
Code Type Country of origin TEQbio (µg/kg,dm) TEQPAHs (µg/kg ,dm)
Code Type Country of origin TEQbio (µg/kg,dm) TEQPAHs (µg/kg,dm)
1
A
Belgium
3.6E-01
6.0E-01
1
B
Belgium
6.4E-01
2.1E-01
2
A
France
1.4E-01
4.5E-02
2
B
France
2.9E-01
1.0E-01
3
A
France
5.7E-01
2.0E-01
3
B
Luxembourg
2.0E+00
1.2E+00
4
A
Finland
1.2E-01
3.9E-02
4
B
Belgium
3.8E+00
2.5E-01
5
A
Italy
3.3E-01
5.0E-01
5
B
The Netherlands
3.8E-01
7.1E-02
6
A
Luxembourg
6.5E-01
4.5E-01
6
B
The Netherlands
5.7E-01
1.9E-01
7
A
Belgium
2.7E+00
2.1E-01
7
B
Spain
1.6E-01
3.2E-02
8
A
The Netherlands
4.4E-01
2.1E-01
8
B
Sweden
1.1E+00
1.5E-01
9
A
Spain
<1.0E-02
4.4E-02
9
B
Denmark
8.8E-01
6.2E-02
10
A
Sweden
4.1E-01
6.7E-02
10
B
Germany
5.1E-01
1.1E-01
11
A
The Netherlands
1.4E+00
1.8E-01
11
B
Germany
6.5E-01
8.5E-02
12
A
Denmark
1.8E-01
7.7E-02
12
B
France
1.4E+00
1.7E-01
13
A
Germany
8.6E-01
1.4E-01
13
B
France
1.3E-01
1.3E-01
14
A
Germany
5.2E-01
2.0E-01
14
B
France
1.5E+00
6.1E-01
15
A
Germany
1.1E+00
1.1E-01
15
B
France
2.7E-01
1.4E-01
16
A
Germany
5.3E-01
8.3E-01
16
B
France
1.4E+00
1.7E-01
17
A
France
4.8E-01
2.9E-01
17
B
France
7.3E-01
1.1E-01
18
A
Germany
1.1E+00
1.8E-01
18
B
France
1.2E+00
2.5E-01
19
A
Italy
4.7E-01
7.5E-02
19
B
Belgium
6.0E-01
1.8E-01
20
A
Italy
1.2E+00
1.1E-01
20
B
Belgium
2.7E+00
1.9E+00
21
A
Italy
1.2E-01
4.3E-02
21
B
Suisse
2.4E-01
1.2E-01
22
A
Portugal
5.6E-01
6.3E-02
22
B
Italy
2.1E-01
3.9E-02
23
B
France
2.5E-01
6.6E-02
23
A
Belgium
3.3E+00
1.6E-01
24
A
United Kingdom
1.2E+00
1.7E-01
25
A
Suisse
6.4E-01
1.8E-01
26
A
Suisse
1.4E+00
3.5E-01
27
A
Germany
1.2E+00
1.5E-01
28
A
Belgium
2.0E+00
3.6E-01
Code Type Country of origin TEQbio (µg/kg,dm) TEQPAHs (µg/kg,dm)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
1
2
3
4
5
6
7
8
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
D
D
D
D
D
D
D
D
France
Finland
Luxembourg
Spain
Germany
Austria
Austria
Austria
France
France
France
France
France
France
Czech Rep.
United Kingdom
France
France
France
France
France
Portugal
Portugal
United Kingdom
<1.0E-02
4.8E-01
4.4E+00
3.3E-01
1.1E+00
1.1E+00
4.5E-01
1.2E+00
2.8E-01
1.8E+00
4.4E-01
5.4E-01
2.9E-01
2.7E-01
1.6E+00
9.5E-01
5.6E-01
2.3E-01
6.4E-01
6.2E-01
1.3E+00
4.7E-01
1.6E-01
9.6E-01
9.9E-02
2.0E-01
2.0E+00
5.8E-02
1.8E-01
1.4E-01
1.0E-01
1.7E-01
9.2E-02
1.5E-01
2.1E-01
1.4E-01
5.9E-02
1.9E-01
6.7E-01
2.3E-01
8.1E-02
6.2E-02
1.4E-01
9.7E-02
1.1E-01
5.2E-02
5.2E-02
2.9E-01
Code Type Country of origin TEQbio (µg/kg,dm) TEQPAHs (µg/kg,dm)
1
2
3
4
5
1
1
2
1
2
3
4
5
F
F
F
F
F
G
H
H
i
i
i
i
i
Belgium
Luxembourg
Austria
Belgium
Belgium
Austria
Netherlands
France
France
Netherlands
Austria
Austria
France
<1.0E-02
3.4E-01
5.0E-02
4.6E-01
<1.0E-02
9.0E-02
1.3E+00
1.2E+00
5.6E-01
8.2E+00
6.3E+00
3.7E-01
2.6E-01
6.6E-02
1.2E-01
1.0E-02
1.3E-01
1.0E-01
1.2E-01
3.0E-01
1.8E-01
1.2E-01
2.8E+00
1.3E-01
1.4E-01
1.7E-01
Legend: A-Biobin + green waste compost, B – green waste compost, C- sewage sludge compost, D – MBT compost, F – manure + biowaste digestate, G – manure + energy crops digestate, H –
MBT digestate, i – Other; TEQbio- toxic equivalent of 2,3,7,8 tetrachlorodibenzo-p-dioxin calculated from bioassay; TEQPAH – toxic equivalent of 2,3,7,8 TCDD for PAHs calculated from
analytical results and induction equivalency factors for PAHs, dm-dry mass
Values of TEQbio are average of three replicates, CV<30%, in italic are signed TEQsPAH higher than TEQbio
Fig. S1 Dose-response curve of standard compound – 2,3,7,8-TCDD and one of selected sample (C3) before and after sulphur acid treatment
TCDD calibration
Sample C3
raw extract
H2SO4 treated
% TCDD 500pM
% TCDD 500pM
100
100
50
0
-13
50
0
-12
-11
log c (M)
-10
-9
-6
-5
-4
-3
log c (g/ml)
-2
-1