Chemosphere 93 (2013) 14711478

Contents lists available at SciVerse ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Trends of PCDD/F and PCB concentrations and depositions in ambient

air in Northwestern Germany
Peter Bruckmann a,, Ernst Hiester a, Marcel Klees a, Cornelius Zetzsch b
a
b

North-Rhine Westphalian State Agency for Nature, Environment, and Consumer Protection (LANUV NRW), Wallneyer Str. 6, 45133 Essen, Germany
University of Bayreuth, Research Center for Atmospheric Chemistry, Dr. Hans-Frisch-Str. 1-3, 95440 Bayreuth, Germany

h i g h l i g h t s
 Time series of PCDD/F concentrations in ambient air and depositions are presented.
 PCB concentrations in ambient air decay only slightly.
 Half-lives for PCDD/F and for the sum of the six indicator PCB could be calculated.
 Removal of PCDD/F and PCB in the atmosphere is slowed down by secondary emissions.
 Input of PCDD/F via the air path will continue for another decade in conurbations.

a r t i c l e

i n f o

Article history:
Received 28 January 2013
Received in revised form 14 June 2013
Accepted 16 July 2013
Available online 16 August 2013
Keywords:
PCDD/F
PCB
Time series
Concentration in ambient air
Deposition
Half-lives

a b s t r a c t
Time series of polychlorinated dioxins and furans (PCDD/F) and polychlorinated biphenyls (PCB) in ambient air of a large conurbation in North-Western Germany are presented and analyzed. The trend of PCDD/
F concentrations, starting from as early as 1988, shows a pronounced decrease by at least one order of
magnitude, demonstrating that the emission reductions were effective. The PCDD/F depositions also have
decreased by a factor of 5 since 1992. However, both trends have leveled out since 2005. Time series of
PCB concentrations and depositions starting in 1994 show only slight decreases for the concentrations
and almost no decrease for the depositions. From the decay rates following rst order kinetics, half-lives
in the order of 5-15 years for the PCDD/F and 15-31 years for the sum of the six indicator PCB could be
calculated, which are much longer than the half-lives estimated from their reactivity towards the OH radical. Apparently, small fresh emissions (PCDD/F), considerable secondary emissions and evaporation from
contaminated soils slow down their decay in the atmosphere of big conurbations. Analyzing the decay
rates of individual PCB congeners shows that the lower chlorinated and more volatile ones are removed
faster than the higher chlorinated congeners, probably via gas phase reactions with the OH radical. It can
be concluded from the present study that the input of PCDD/F and PCB into the food chain via the air path
will continue for another one or two decades in big conurbations.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
The high toxicity of polychloriated dibenzodioxins (PCDD) and
dibenzofurans (PCDF) (Safe, 1990) has given rise to comprehensive
regulations to control their emissions. Particularly the introduction
of a strict emission limit of 0.1 ng m3 I-TEQ (toxic equivalents
(NATO CCMS, 1988)) in 1990 for waste incineration plants
(Siebzehnte Verordnung, 1990), in European waste incinerators
(Directive 2000/76/EG, 2000) and for industrial installations, such
as sintering plants in 2002 (Technische Anleitung zur Reinhaltung
der Luft nach BImSchG, 2002) has effectively reduced their emissions by more than one order of magnitude. Taking the emission
Corresponding author. Tel.: +49 201 7995 1257; fax: +49 201 7995 1575.
E-mail address: peter.bruckmann@lanuv.nrw.de (P. Bruckmann).
0045-6535/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.chemosphere.2013.07.029

inventory in Northwestern Germany (state of Northrhine-Westphalia) as an example, the annual emissions of industrial sources
decreased from 136 g I-TEQ in 1996 to 13 g I-TEQ in 2008 (LANUV
NRW, 2012).
Also polychlorinated biphenyls (PCB), which were produced
since 1929 for various technical applications, were strictly regulated when serious health effects became apparent in 1968 after
the consumption of polluted rice oil in Japan, causing the Yusho
disease, and in 1979 in Taiwan, becoming known as Yu Cheng disease (Chen and Hites, 1983; Maguda and Yoshimura, 1984). Estimated quantities produced and distributed in Germany since
1929 amount to 24 000 tons for open applications, such as paints,
sealing material or small capacitors in household goods, and to
59 000 tons for closed applications such as large condensers and
transformer stations. The application in open technical systems

1472

P. Bruckmann et al. / Chemosphere 93 (2013) 14711478

was prohibited in 1978 in Germany (Verbot des Inverkehrbringens

von PCB, Zehnte Durchfhrungsverordnung, 1978), and the production of PCBs came to an end in 1988 (Verordnung zum Verbot
von polychlorierten Biphenylen, polychlorierten Terphenylen und
zur Beschrnkung von Vinylchlorid, 1989). Internationally, PCBs
were regulated in 2001 by the Stockholm convention on persistent
organic pollutants (2001).
Due to the regulations, one might assume that PCBs, PCDDs and
PCDFs no longer pose a danger to the environment, as fresh
emissions would be greatly reduced (PCDD/Fs) or stopped (PCBs).
However, the European thresholds, xed for dioxins, furans and
coplanar PCBs in meat, fat and eggs (European Commission, 2006
and European Commission, 2011), are still exceeded at times
(EG/1259/2011 and EG/1881/2006), even if a direct contamination
of fodder or high PCDD/F or PCB levels in the ground can be ruled
out. This is predominantly the case for livestock and chickens kept
outdoors in or near big conurbations. In particular, coplanar PCBs
addition to TEQ values exceed these thresholds. It appears that
the background pollution in densely habitated areas is still sufcient to give rise to exceedances of European thresholds for consumer protection in meat and fat.
Besides contaminated sediments adjacent to and along rivers or
locally by efuents from landlls or other contaminated material
brought into the soil, previous and present concentrations and
depositions of chlorinated compounds in ambient air are an important input route into the environment. Trends extending over two
decades would shed some light on the following questions:
Is the signicant decrease of emissions (PCDD/F) or the halt in
the production (PCBs) reected by the trends, and have the
abatement measures been successful?
Do concentrations and depositions decrease further or is there
an ongoing input into the environment via the air path and
what are the current lifetimes?
Trends in dioxins and furans in ambient air (Katsoyiannis et al.,
2010) and other media (Lead et al., 1996; Green et al., 2001) have
been studied in several countries mostly at rural sites in the framework of the EMEP programme (Lead et al., 1996; Green et al., 2001;
Katsoyiannis et al., 2010). One of the longest time series in ambient
air beginning in 1991 at six sites in the UK (3 urban, 3 rural/semirural sites) showed an exponential decay with atmospheric halflives between 3.2 and 5.9 years, whereas at rural sites there was
no discernible change since 1996 (Katsoyiannis et al., 2010). At
the same sites in the UK, also temporal trends for polychlorinated
biphenyls (PCB) starting in 1991 were measured (Schuster et al.,
2010). They found an average half-life, averaged over the 6 indicator PCBs (Ballschmiter and Zell, 1980), of 4.7 years in ambient air.
Extending the measurements to 6 remote locations in Norway
and 5 rural or remote stations in the UK, an average lifetime of
8.4 years has been reported (Schuster et al., 2010).
Trends for 83 polychlorinated biphenyl congeners since 1990
were also investigated at several sites near the North American
Great Lakes (Venier and Hites, 2010). The concentrations of the
PCBs in air decreased with an overall half-life of 17 2 years. The
authors concluded that this remarkably slow decay after the banning of the compounds over 30 years ago is probably due to large
amounts of PCBs in transformers, capacitors and other electrical
equipment and in storage and disposal facilities that are slowly
leaking into the atmosphere. More recently, half-lives of about
8 years for the PCB-18 congener and >50 years for the PCB-52 congener were determined from measurements in Chicago, whereas at
the remote site Eagle Harbour, the half-lives were about 10 years
(PCB-18) and 18 years (PCB-52), respectively (Venier et al., 2012).
Long-term trends for PCB patterns PCB-28, 101, 153 and 180 from
1950 to 2010 have been reviewed and studied on a continental and

intercontinental scale using a global atmosphereocean general

circulation model, considering atmospheric long-range transport
(Stemmler and Lammel, 2012; Lammel and Stemmler, 2012). A
downwind shift of the burden maxima in terrestrial compartments
(soil and vegetation) is observed with regard to the westerlies for
Eurasia (but interestingly upwind for North America, due to other
peculiarities) and always northwards in the northern hemisphere
in the sense of a global distillation and more pronounced for the
lighter PCBs with less Cl substituents (Stemmler and Lammel,
2012). Inter-continental transport from Eurasia was found to account largely for the contamination of Alaska and British Columbia.
As atmospheric lifetimes are a complex result of primary and
secondary emissions and sink processes such as deposition and
immobilization on the ground or decay in the atmosphere, they depend on proximity to major source areas. Trends in densely industrialized and inhabitated areas close to sources are not confounded
by long range transports and show the effects of reduction measures more distinctively. On the other hand, present input into
the environment by diffuse sources may slow down the apparent
decay of the persistent chlorinated compounds. To get as complete
an overview as possible, time trends from various locations
(remote ones and near to sources) are therefore needed.
In this work, we report on long term series for dioxins, furans
and PCBs in the densely habitated Rhine-Ruhr conurbation in
Northwestern-Germany. Measurements (annual means) of dioxin
and furan concentrations started already in 1988 at four sites, making this trend one of the longest available to our knowledge.
2. Materials and methods
2.1. Sampling of concentrations and deposition
Ambient air samples (approximately 1000 m3) were collected
monthly in accordance to VDI 3498-1 (07.2002) at the sampling
sites described in Section 3.1 for the determination of PCB and
PCDD/F. As sampling and analysis include the particulate as well
as the gaseous phase, the concentration measurements are not
inuenced by gas particle partitioning. The particulate phase was
sampled on a breglass lter (GFF) and the gaseous phase on
two polyurethane foams (PUF). The sampling period consisted of
1 month each with a sampling rate of 2.2 m3 h1 and sampling
intervals of 40 min per hour. After sampling, the GFFs and the PUFs
were stored at laboratory conditions until analysis.
Deposition samples (bulk deposition) were collected in accordance to VDI 2090-1 (01.2001). Six suitable glass jars were positioned at each sampling site and collected monthly. After
sampling, the covered glass jars were stored at laboratory conditions until analysis.
2.2. Analysis
The Soxhlet extracts were subjected to a cleanup procedure.
Following DIN EN 1948-2 (06.2006), multi-layer solid phase chromatography with silica modied with H2SO4, NaOH and AgNO3 as
reaction agents were applied as primary clean-up step. The lled
chromatography column was pre-washed with n-hexane before
the sample was applied to this column. The elution of the analytes
of interest was performed with n-hexane. The eluate was concentrated to 5 mL via rotary evaporation. Subsequently, a basic alumina column was used for the separation of PCB and PCDD/F. To
that end alumina was packed into a chromatography column. Sodium sulfate was added on top of the alumina layer. A fraction of
n-hexane was discarded before the PCB fraction got eluted by toluene. PCDD/F were eluted using 1:1 (v/v) n-hexane/dichloromethane. The PCB fraction was subsequently separated into two

P. Bruckmann et al. / Chemosphere 93 (2013) 14711478

fractions on active carbon. The rst fraction consists of the PCB

congeners #28, #52, #101, #138, #153, #180 and the dioxin-like
PCB congeners #123, #118, #114, #105, #167, #156, #157, #189.
The second fraction consists of the mono-ortho PCB congeners
#77, #81, #126, #169. Before analysis and concentration via a
nitrogen ow to a nal volume of 10 lL (PCDD/F) and 100 lL
(PCB), a PCB and PCDD/F recovery standard was added.
In accordance to DIN EN 1948-4 (10.2012), gas chromatography
(HP/Agilent series) in combination with low resolution quadrupole
mass spectrometry (HP/Agilent series) was used for the analysis of
the indicator PCB #28, #52, #101, #138, #153, #180 and the dioxin-like PCB congeners #123, #118, #114, #105, #167, #156, #157,
#189. Helium 5.0 was used as carrier gas at constant ow. The GC
was equipped with a DB-5 column (J&W) (50 m; 0.20 mm i.d.;
0.11 lm lm thickness). Electron impact was used for ionization
and electron energy was set to 70 eV. Splitless injection temperature was set to 250 C, ion source temperature was set to 280 C
and 1 lL of sample was injected each. The mono-ortho PCB congeners #77, #81, #126, #169 were analyzed using gas chromatography coupled to a high resolution mass spectrometer. The GC was
equipped with an apolar stationary phase such as a DB-5 column
(J&W) (50 m; 0.20 mm i.d.; 0.11 lm lm thickness). Helium 5.0
was used as carrier gas at constant ow with 1.0 mL min1 and
again 1 lL splitless injection was used at 250 C and ion source
temperature was set to 260 C. Electron impact was used for ionization and electron energy was set to 44 eV.
Analysis for all 2,3,7,8-PCDD/F and PCDD/F homologous groups
starting with tetrachlorohomologues was performed in accordance
with DIN EN 1948-2 (06.2006) and DIN EN 1948-3 (06.2006) on a
gas chromatograph and a high resolution sector mass spectrometer
(currently DFS [Thermo Scientic]; before 2009 comparable sector
mass spectrometers were used). The GC was equipped with a polar
chromatography column (e.g. SP-2331 column (Supelco, Bellefonte, USA) (60 m; 0.25 mm i.d.; 0.20 lm lm thickness)). Helium
5.0 was used as carrier gas at constant ow with 1.0 mL min1.
Splitless injection of 1 lL each was used at a temperature of
250 C and ion source temperature was set to 260 C. Electron impact was used for ionization and electron energy was set to 44 eV.

3. Results and discussion

3.1. Time series of PCDD/F concentrations and depositions
Systematic monitoring of PCDD/F concentrations in ambient air
(annual means) started at 4 sites in 1988 and at an additional site
in 1996. The sites can be characterized as follows: Essen (urban
background), Duisburg-Buchholz and Duisburg-Meiderich (urban
background with some inuence from industrial sources), Dortmund-Mitte (urban background), Kln-Riehl (urban background)
and Duisburg-Wanheim (industrial, in the vicinity of 2 secondary
zinc smelters and one steel works with sintering plant). Four
time series (Essen, Duisburg-Buchholz, Duisburg-Wanheim and
Dortmund-Mitte) span the whole period until 2011, whereas the
measurements at Kln-Riehl were stopped in 1996 and at
Duisburg-Meiderich in 2008. It has to be borne in mind that all
sites are in the densely populated and heavily industrialized
Rhine-Ruhr conurbation. Particularly the air quality in Duisburg
is or was in the past inuenced by heavy industry such as steel
mills and secondary zinc- and copper smelters.
Fig. 1 presents the trends of PCDD/F concentrations at the six
monitoring stations, partly spanning more than 2 decades. The
concentrations are expressed as toxic equivalents (TEQ, up to
2003 according to NATO/CCMS (NATO/CCMS, 1988), from 2004
to 2006 according to WHO-TEQ 1998 (van den Berg et al., 1998),
from 2007 onwards according to WHO-TEQ 2005 (van den Berg

1473

et al., 2006). In general, concentrations of individual congeners exceed a signal to noise ratio of 3:1 and are thus detected during
analysis. In rare cases, at low concentrations, single congeners
were below the limit of detection and were included with half of
the detection limit. This approximation did not signicantly affect
the calculations of TEQ or of annual means.
A pronounced decrease in PCDD/F levels expressed as TEQ by
about one order of magnitude or more (in the case of the industrial
site) can be seen in Fig. 1. The concentrations in 1988 ranged from
130 to 332 fg TEQ m3 (in the case of the industrial site even up to
608 fg TEQ m3 in 1996), whereas the levels in 2011 ranged from
17 to 24 fg TEQ m3. Fig. 1 also shows considerable differences in
PCDD/F concentrations between the stations, which reect the
inuence of industrial sources in the surroundings (weak at the urban background site at Kln, strong at Duisburg). In 2011, the concentration differences between the stations had nearly vanished,
corresponding to the strongly reduced importance of local industrial sources. It can be stated that the abatement measures at the
sources have been successful. The national German target value
of 150 fg WHO-TEQ (including coplanar PCBs (LAI, 2004)), has been
met at all stations since 1999. This also holds true if the concentrations of the dioxin-like (coplanar) polychlorinated biphenyls
(PCB) are included. They currently add 2530% to the sum of TEQ
levels. However, since about 2005, the decrease of dioxin and furan
levels has leveled out. The still ongoing input from fresh emissions (albeit small), the persistence of these compounds in the
atmosphere (compare 3.3) and resuspension from polluted areas
give rise to the current background levels in the atmosphere.
The trends in PCDD/F depositions are shown in Fig. 2. In addition to the urban stations, depositions were also measured at the
rural station Eifel-Simmerath, more than 100 km away from dense
conurbations. Depositions at 5 sites near to industrial facilities at
Duisburg-Wanheim are presented separately in Supplementary
Fig. 1, mainly because of the exceptionally high depositions before
the year 2000, which would have distorted the scale of Fig. 2.
In parallel to the PCDD/F concentrations, the depositions also
decreased considerably within the last 2 decades (about a factor
of 5 at the urban background sites). At the monitoring stations in
the near surroundings of the industrial sources, the decrease was
even more pronounced (about one order of magnitude). The decrease of depositions at the remote site Eifel was smaller, as important local sources are lacking and the levels are dominated by long
range transport. As in the case of the concentrations, depositions
have reached background levels since about 2005, and there is
no further decrease. Note that with the exception of DuisburgBuchholz, which is still somewhat inuenced by industrial sources,
the depositions in the urban background in the Rhine-Ruhr conurbation are comparable with the deposition at the remote site Eifel
(between 10 and 5 pg WHO-TEQ (m2 d)1). This widespread deposition level still exceeds the national German long term objective of
4 pg WHO-TEQ (m2 d)1, including coplanar PCBs, which has been
set with a view to limiting the input of dioxins, furans and coplanar
PCBs into the food chain. Coplanar PCBs contribute between 18.5%
(at the rural station Eifel) and 35.9% at Essen to the total PCDD/F
and PCB burden, expressed as WHO-TEQ (van den Berg et al.,
2006).
3.2. Time series of PCB concentrations and depositions
PCB concentrations in ambient air (sum of the tri- to decachlorbiphenyls, around 194 congeners) were measured at the same 5
sites (Kln, Essen, Dortmund, Duisburg-Meiderich and DuisburgBuchholz, all urban background) and the industrial site of
Duisburg-Wanheim (see Supplementary Fig. 2). At the start of
the measurements in 1994, PCB concentrations at the urban background sites did not differ much, with the exception of somewhat

1474

P. Bruckmann et al. / Chemosphere 93 (2013) 14711478

Fig. 1. Trend of dioxin and furan concentrations in ambient air in the Rhine Ruhr conurbation (annual means).

Fig. 2. Trend of dioxin and furan depositions in the Rhine-Ruhr conurbation and at one remote site (annual means). National German long term objective 4 pg WHOTEQ(PCDD+PCDF+PCB) (m2*d)1.

higher levels (about a factor of 2) at Duisburg-Buchholz and from

2005 to 2009 also at Dortmund. These higher concentrations point
to primary or secondary sources nearby. For Dortmund, the main
source could be identied as a recycling facility for big industrial
transformers, which was closed in 2010 (Bruckmann et al., 2011).
In the case of Duisburg-Buchholz, this additional source could
not yet be identied.
The concentrations decreased only slightly during the last 2
decades, although there were no fresh emissions. However, it has
been shown that numerous recycling facilities and scrap metal
sites (e.g. from industrial and household transformers) give rise
to considerable emissions of PCB laden dust into the atmosphere
(Schwerpunktinspektionsprogramm, PCB, 2012).
Contrary to the dioxins/furans with decreasing fresh emissions
(reaching background levels not before 2005), it can be assumed
that PCB concentrations had already reached their background levels in 1994 at the beginning of the measurements and decayed

only slowly afterwards due to their persistence (see Section 3.3)

and ongoing primary and secondary emissions.
A more commonly used parameter for PCBs is the sum of the 6
indicator PCBs according to Ballschmiter and Zell (1980). This sum
also decreased slightly during the last 2 decades with a rate of
approximately 3% per year (see Fig. 3) for the three urban background stations Essen-Vogelheim, Dortmund-Mitte and Duisburg-Buchholz. The decrease at Dortmund-Mitte is smaller and
shows large annual variations, pointing at the input of local
sources (see above).
There is no clear trend in the deposition of PCBs (sum of tri- to
decachlorobiphenyls, see Supplementary Fig. 3). There are considerable variations between years and stations, which may obscure a
trend. It appears that emissions from used PCBs and resuspension
from contaminated soils and sites add to the annual variations,
particularly at Dortmund and Duisburg-Meiderich with several
scrap metal sites in their surroundings.

1475

P. Bruckmann et al. / Chemosphere 93 (2013) 14711478

Fig. 3. Trend of the 6 indicator PCBs according to Ballschmitter (PCB 28, 52, 101, 138, 153 and 180) at the urban background sites Essen-Vogelheim, Duisburg-Buchholz and
Dortmund-Mitte.

3.3. Trends of individual congeners

PCBs and PCDD/Fs may be removed from the atmosphere by
wet and dry deposition and/or by reaction with OH radicals in
the gas phase (Atkinson, 1990, 1991, 1996). Long-range transport
in the atmosphere is a well-known phenomenon for persistent organic pollutants (Lammel et al., 2011), and once fresh emissions
have been stopped, revolatilisation leads to a shift of the concentration maxima of each semivolatile pollutant towards northern
latitudes and may change the prole. The atmospheric chemistry
of PCBs and PCDD/Fs has been reviewed in detail by Atkinson
(1996), considering gas/particle partitioning, wet and dry deposition and chemical transformation by direct photolysis, reaction
with ozone, OH and NO3 radicals in the gas phase and catalytic
transformation in the particle phase, coming to the conclusion that
reaction with OH is clearly the predominating loss process in the
gas phase. Adopting an estimation method, suggested by Zetzsch
(1982) who recommended employing the Hammett equation with
substituent constants for electrophilic addition, r+, obtained by
Brown and Okamoto (1958) from extensive experiments on various types of reactions and long standing experience, Atkinson
(1996) derived tropospheric lifetimes of PCBs and PCDD/Fs with

up to 6 Cl atoms, ranging from about 12 d for the non-chlorinated

biphenyl, dioxin and furan to 120 d for the hexachlorinated PCDFs
were calculated. The low volatility limits experimental determination of the rate constants to congeners with less than 6 Cl substituents. The unchlorinated congeners were studied by Zetzsch
(1982), Atkinson (1984), Atkinson and Aschmann (1985), Klpffer
et al. (1986) and Anderson and Hites (1996) for biphenyl and Kwok
et al. (1994, 1995) for dibenzo-p-dioxin and dibenzofuran, and a
range of mono- di-, tri-, tetra- and pentachlorobiphenlys were
studied by Atkinson and Aschmann (1985), Kwok et al. (1995)
and Anderson and Hites (1996). From the available laboratory
and ambient air data, lifetimes for the highly chlorinated PCBs,
PCDDs and PCDFs predominantly present in the particulate phase
and mainly removed by wet and dry deposition were estimated between 5 and 30 d, whereas lifetimes for lower chlorinated compounds mainly removed by reactions with the OH radical ranged
from 1 to 50 d (Aktinson, 1996). Evidence for the degradation of
PCBs with the number 4, 7, 15, 28, 31, 44, 47 and 110 in urban
air by OH has been obtained from a comparison of day/night levels
of PCBs and the number of Cl substituents on the congeners (Totten
et al., 2002). Further evidence for the destruction of PCBs by OH
radicals during long-range transport from the Black Sea over the

Table 1
OH rate constants kOH (1012 cm3 molec.1 s1) and tropospheric half-lives (days, assuming an average OH radical daylight concentration over 12 h
per day of 1.5  106 radicals per cm3) of selected PCDDs/PCDFs/PCBs, calculated by the program AOP 1.92 using the Hammett equation (Zetzsch,
1982; Kwok and Atkinson, 1995a,b).

PCDDs/PCDFs

PCB

2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
OCDD
OCDF
PCB-28: 2,4,4-trichlorobiphenyl
PCB-52: 2,2,5,5-tetrachlorobiphenyl
PCB-101: 2,2,4,5,5-pentachlorobiphenyl
PCB-138: 2,2,3,4,4,5-hexachlorobiphenyl
PCB-153: 2,2,4,4,5,5-hexachlorobiphenyl
PCB-180: 2,2,3,4,4,5,5-heptachlorobiphenyl

kOHa

Half-lifea

0.7530
0.2531
0.1147
0.1147
0.0542
0.0107
1.1856b
0.7301
0.33485
0.1640
0.1640
0.1046

14.204
42.258
93.244
93.244
197.438
1001.728
9.022
14.649
31.947
65.219
65.219
102.248

a
The numerous digits, given for the rate constants and the half-lives, are a convention to mark values obtained from structure/reactivity
relations in clear distinction from values obtained from experiments.
b
For PCB-28, kOH = 1.1 was determined experimentally (Anderson and Hites, 1996).

1476

P. Bruckmann et al. / Chemosphere 93 (2013) 14711478

Eastern Mediterranean were obtained from diurnal proles of PCBs

8, 31, 20 + 33, 47 + 48, 44, 95 and 110 by Mandalakis et al. (2003).
From diurnal variations in gas-phase concentrations for selected
PCB congeners, measured in several North American cities, a faster
daytime depletion of the lower chlorinated biphenyls in relation to
the octa- and nonachlorobiphenyl congeners was observed. As the
reactivities of partly and fully chlorinated congeners with the OH
radical are expected to differ by more than one order of magnitude
(compare Table 1), trends for individual congeners with different
reactivities and vapor pressures should give some information on
the removal mechanism. If the chlorinated compounds are mainly
removed via gas-phase reactions, lower chlorinated compounds
with higher reactivities and vapor pressures should be removed
faster than highly chlorinated congeners with low reactivities
and vapor pressures. The opposite should be observed if deposition
to the soil were the main sink, as lower chlorinated compounds
with higher vapor pressures can more easily re-evaporate into
the gas phase. It has been shown that the tri- and tetrachlorinated
PCBs are predominantly found in the gas phase, whereas hexa- and
higher chlorinated PCBs are mainly bound to particles (see also
Fig. 5).

Fig. 4 and Supplementary Table 1 show individual trends for the

six indicator PCBs (Ballschmiter and Zell, 1980) PCB-52, 28, 101,
153, 138 and 180 and of four individual PCDD/F congeners at the
3 urban background locations at Duisburg-Buchholz, Essen-Vogelheim and Dortmund-Mitte (logarithmic scale). It can be seen that
the lower chlorinated congeners PCB-28 and 52 with higher reactivities decay faster than the higher chlorinated congeners 138,
153 and 180, which remain nearly constant over time. The regression equations for the six indicator PCBs at the three background
stations Essen-Vogelheim, Duisburg-Buchholz and Dortmund-Mitte as well as the regression equations for four individual PCDD/F
congeners in Supplementary Table 1 decrease at approximately
the same rate.
The straight lines in the logarithmic scale (see Fig. 4 at EssenVogelheim) indicate that the removal of the lower chlorinated
congeners 28 and 52 follows rst order kinetics.

PCBt PCB0  ekt :

From the slopes k, the half-lives of the congeners in the ambient

air of the Rhine-Ruhr conurbation, can be calculated:

t1=2 ln 2=k

Fig. 4. Trend of the individual PCB congeners PCB 28, 52, 101, 138, 153 and 180 at the urban background site Essen-Vogelheim.

Fig. 5. Annual cycle (2010) for PCB 28, 52, 101, 153, 138 and 180 at the station Essen-Vogelheim.

P. Bruckmann et al. / Chemosphere 93 (2013) 14711478

Table 2
Half-lives of the decrease of PCBs/PCDDs/PCDFs in the ambient air of the Rhine-Ruhr
conurbation (years).
Congener

Essen

Duisburg-Buchholz

Dortmund-Mitte

PCB28
PCB52
PCB101
PCB153
PCB138
PCB180
OCDD
OCDF
2,3,7,8-TCDF
2,3,7,8-TCDD

7.3
9.2
41.8
256
92
330
16.9
76.2
13.7
10.6

15.7
12.9
32.7
29
25.7
30.8
7.4
6.0
8.7
6.1

13.1
16.9
No decline
153.8
No decline
No decline
8.9
6.9
7.3
5.9

Half-lives of selected PCDD/F and PCB congeners have been calculated from the slopes for 3 stations, see Table 2.
In contrast to Schuster et al. (2010), who did not nd signicant
differences between the half-lives of individual PCB congeners, the
data in Table 2 demonstrate considerably shorter half-lives for the
lower chlorinated congeners PCB-28 and 52 compared to the higher chlorinated ones. Shorter half-lives for the low chlorinated
PCB-28 congener in comparison to the higher chlorinated PCB-52
congener (Venier et al., 2012) and a faster decay of lower chlorinated PCBs during daylight hours (Totten et al., 2002) have also
been derived from monitoring data from the North Eastern United
States. This is consistent with the trend in the half-lives in Table 1
calculated for reactions with the OH radical and with the assumption that this reaction is indeed one important removal mechanism
for the less chlorinated PCB-28 and PCB-52. However, the half-lives
are much longer than predicted by Table 1, demonstrating that still
ongoing primary and secondary emissions are strongly slowing
down the removal from the atmosphere. The half-lives are also
considerably longer than those calculated for the sum of the 6 indicator PCBs by Schuster et al. (2010) from air samples taken at six
rural and urban monitoring sites (half-lives between 3.1 and
6.3 years compared to 1531 years in this study), but are similar
to those determined around the Great Lakes (about 60 years for
PCB-52 (Venier et al., 2012) and 17 years for the sum of PCBs
(Venier and Hites, 2010). The considerably longer half-lives in or
near conurbations compared to rural or remote areas underpin
the conclusion already drawn by Venier and Hites, 2010 that large
amounts of PCBs in transformers, capacitors and other electrical
equipment in use or kept in storage and even more so disposed
of in facilities are still slowly leaking into the atmosphere. The
longer half-lives for PCB congeners in Dortmund-Mitte with identied emissions from an industrial transformer recycling facility
compare nicely with this assumption.
The removal of the PCDD/Fs (Table 2 and Supplementary
Table 1) does not show the differences in their decay rates predicted by their gas-phase chemistry. Obviously, other factors such
as the strong decline of primary dioxin and furan emissions during
the rst years of the time series, still ongoing (albeit small) fresh
emissions and secondary emissions from diffusive sources govern
their concentrations and removal rates.
The exchange of semivolatile organic compounds between the
compartments air and soil has intensively been studied (Hippelein
and McLachlan, 1998, 2000; Cousins and Jones, 1998; Wong and
Bidleman, 2011). Considering the large reservoir of PCBs and
PCDD/Fs in soils and the reduction of primary emissions for these
compounds, calculated air/soil partitioning especially for lower
chlorinated compounds (e.g. PCB-52) has established the relevance of historically contaminated soils as secondary source into
the atmosphere. This is one reason for the mismatch between theoretical atmospheric removal and observed gas-phase
concentrations.

1477

The fact that tri- and tetrachlorinated PCB congeners are predominantly found in the gas phase and are therefore exposed to
reactions with the OH radical can also be taken from Fig. 5, showing annual cycles of PCB congeners at the site Essen-Vogelheim for
the year 2010. The higher levels of the low boiling PCB congeners
during the warm summer months with stronger evaporation are
apparent, in contrast to annual cycles of most air pollutants which
show their maxima in wintertime due to reduced dispersion
conditions.
4. Conclusions
With ongoing primary and secondary emissions, it will take
about two decades or more until concentrations and depositions
of PCBs in the ambient air of the Rhine-Ruhr region and other
conurbations will have decreased by a further factor of 2.
The PCB mixture in ambient air will be enriched by higher chlorinated congeners over time (Supplementary Fig. 4). The contribution of tri- and tetrachlorobiphenyl with shorter lifetimes in the
atmosphere to the sum of the six indicator PCBs is decreasing,
whereas the opposite holds true for the higher chlorinated
congeners.
At a rst glance, this result is surprising, as street dusts from
industrial premises and ambient air sampled near industrial diffuse sources have comparably high contents of tri- and tetrasubstituted PCBs (Klees, in preparation). However, this greater input is
counterbalanced by the faster decay in the atmosphere.
Also the levels of dioxins and furans are currently only slowly
decreasing, with half-lives of the order of 515 years. Consequently, the problems arising from the input of dioxins, furans
and PCBs into the food chain will continue for a decade or longer,
even when fresh emissions have been stopped (PCBs) or greatly
reduced (dioxins and furans). These results give important implications for regulators, demonstrating that input of persistent POPs
into the food chain will continue for about two decades.
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.
2013.07.029.
References
Aktinson, R., 1996. Atmospheric chemistry of PCBs, PCDDs and PCDFs. In: Hester,
R.E., Harrison, R.M., Atkinson, R. (Eds.), Chlorinated Organic Micropollutants
Atmospheric Chemistry of PCBs, PCDDs and PCDFs. Royal Society of Chemistry
(ISBN: 978-1-84755-049-1, doi: 10.1039/9781847550491-00053).
Anderson, P.N., Hites, R.A., 1996. OH radical reactions: the major removal pathway
for polychlorinated biphenyls from the atmosphere. Environ. Sci. Technol. 30,
17561763.
Atkinson, R., 1984. Kinetics of the reactions of naphthalene and biphenyl with OH
radicals and with O3, at 294 1 K. Environ. Sci. Technol. 18, 110113.
Atkinson, R., 1990. Gas-phase troposphere chemistry of organic compounds: a
review. Atmos. Environ. 24A, 141.
Atkinson, R., 1991. Atmospheric lifetimes of dibenzo-p-dioxins and dibenzofurans.
Sci. Total Environ. 104, 1733.
Atkinson, R., Aschmann, S., 1985. Rate constants for the gas-phase reaction of
hydroxyl radicals with biphenyl and the monochlorobiphenyls at 295 1 K.
Environ. Sci. Technol. 19 (5), 462464.
Ballschmiter, K., Zell, M., 1980. Analysis of polychlorinated biphenyls (PCB) by glass
capillary gas chromatography. Fresenius Z. Anal. Chem. 302, 2023.
Bericht des Lnderausschusses fr Immissionsschutz (LAI) Bewertung von
Schadstoffen fr die keine Immissionswerte festgelegt sind. 21.09.04.
Brown, H.C., Okamoto, Y., 1958. Electrophilic substituent constants. J. Am. Chem.
Soc. 80, 49794987.
Bruckmann, P., Hiester, E., Klees, M., 2011. Die Umweltbelastung durch polychlorierte
Biphenyle (PCB) im Dortmunder Hafen. Gefahrstoffe Reinhaltung der Luft 71 Nr.
4.
Chen, P., Hites, R., 1983. Polychlorinated biphenyls and dibenzofurans retained in
the tissues of a deceased patient with Yu Cheng in Taiwan. Chemosphere 12,
15071516.

1478

P. Bruckmann et al. / Chemosphere 93 (2013) 14711478

Commission Regulation (EC) No. 1881/2006 of 19 December 2006 setting maximum

levels for certain contaminants in foodstuffs. Ofcial Journal of the European
Union L 364/5.
Commission Regulation EC No. 1259/2011 of 2 December 2011 amending
Regulation (EC) No 1881/2006 as regards maximum levels of dioxins, dioxinlike PCBs and non dioxin-like PCBs in foodstuffs. Ofcial Journal of the European
Union L 320/18.
Cousins, I.T., Jones, K.C., 1998. Airsoil exchange of semi-volatile compounds (SOCs)
in the UK. Environ. Pollut. 102, 105118.
DIN EN 1948-2 (06.2006). Stationary source emissions determination of the mass
concentration of PCDDs/PCDFs and dioxin-like PCBs Part 2: Extraction and
clean-up of PCDDs/PCDFs; German version EN 1948-2:2006.
DIN EN 1948-3 (06.2006) Stationary source emissions Determination of the mass
concentration of PCDDs/PCDFs and dioxin-like PCBs Part 3: Identication and
quantication of PCDDs/PCDFs; German version EN 1948-3:2006.
DIN EN 1948-4 (10.2012) Stationary source emissions Determination of the mass
concentration of PCDDs/PCDFs and dioxin-like PCBs Part 4: Sampling and
analysis of dioxin-like PCBs; German version EN 1948-4:2010.
Directive 2000/76/EC of the European Parliament and of the council of 4 December
2000 on the incineration of waste. Ofcial Journal of the European Communities
L 332/91.
Green, N.J.L., Jones, J.L., Jones, K.C., 2001. PCDD/F deposition time trend to Esthwaite
Water, UK and its relevance to sources. Environ. Sci. Technol. 35, 28822888.
Hippelein, M., McLachlan, M., 1998. Soil/Air partitioning of semivolatile organic
compounds. 1. Method development and inuence of physicalchemical
properties. Environ. Sci. Technol. 32, 310316.
Hippelein, M., McLachlan, M., 2000. Soil/air partitioning of semivolatile organic
compounds. 2. Inuence of temperature and relative humidity. Environ. Sci.
Technol. 34, 35213526.
Katsoyiannis, A., Gioia, R., Sweetman, A.J., Jones, K.C., 2010. Continuous monitoring
of PCDD/Fs in UK Atmosphere: 19912008. Environ. Sci. Technol. 44, 5735
5740.
Klpffer, W., Frank, R., Kohl, E.-G., Haag, F., 1986. Quantitative Erfassung der
photochemischen Transformationsprozesse in der Troposphre. Chemiker
Zeitung 110, 5762.
Kwok, E.S.C., Atkinson, R., 1995. Estimation of hydroxyl radical reaction rate
constants for gas-phase organic compounds using a structure-reactivity
relationship: an update. Atmos. Environ. 29, 16851695.
Kwok, E.S.C., Arey, J., Atkinson, R., 1994. Gas-phase atmospheric chemistry of
dibenzo-p-dioxin and dibenzofuran. Environ. Sci. Technol. 28, 528533.
Kwok, E.S.C., Atkinson, R., Arey, J., 1995. Rate constants for the gas-phase reactions
of the OH radical with dichlorobiphenyls, 1-chlorodibenzo-p-dioxin, 1,2dimenthoxybenzene, and di phenyl ether: Estimation of OH radical reaction
rate constants for PCBs, PCDDs, and PCDFs. Environ. Sci. Technol. 29, 1591
1598.
Lammel, G., Stemmler, I., 2012. Fractionation and current time trends of PCB
congeners: evolvement of distributions studied using a global atmosphereocean general circulation model. Atmos. Chem. Phys., 71997213.
Lammel, G., Palm, W.-U., Zetzsch, C. In: Chemie ber den Wolken (ed. R. Zellner) and
Gesellschaft Deutscher Chemiker), Was und wo sind POPs? Wiley-VCH,
Weinheim, 2011. pp. 211220.
LANUV NRW, 2012. Emission Inventory under <www.lanuv.nrw.de/emikat97/
startfr2.htm>.
Lead, W.A., Steinnes, E., Jones, K.C., 1996. Atmospheric deposition of PCBs to moss
(Hylocomium splendens) in Norway between 1977 and 1990. Environ. Sci.
Technol. 30, 524530.
Maguda, Y., Yoshimura, H., 1984. Polychlorinated biphenyls and dibenzufurans in
patients with Yusho and their toxicological signicance: a review. Am. J. Ind.
Med. 5, 3144.
Mandalakis, M., Berresheim, H., Stephanou, E.G., 2003. Direct evidence for PCB
destruction in the subtropical troposphere by OH radicals. Environ. Sci. Technol.
37, 542547.

NATO/CCMS (North Atlantic Treaty Organisation/Committee on the Challenge of

Modern Society) International toxicity equivalence factors (I-TEF) method of
risk assessment for complex mixtures of dioxins and related compounds, 186,
1988.
Safe, S., 1990. Polychlorinated biphenyls (PCBs) dibenzo-p-dioxins (PCDDs) and
dibenzofurans (PCDFs and related compounds: environmental and mechanistic
considerations which support the development of toxic equivalent factors
(TEFs). CRC Crit. Rev. Toxicol. 21, 5188.
Schuster, J.K., Gioia, R., Sweetman, A.J., Jones, K.C., 2010. Temporal trends and
controlling factors for polychlorinated biphenyls in the UK Atmosphere.
Environ. Sci. Technol. 44, 80688074.
Schwerpunktinspektionsprogramm PCB. Inspektion von Anlagen, in denen PCBhaltiger-Abfall anfllt oder entsorgt wird, 2012. LANUV-Fachbericht 39. ISSN
18643930 LANUV-Fachberichte.
Siebzehnte Verordnung zur Durchfhrung des Bundes-Immissionsschutzgesetzes
(Verordnung ber die Verbrennung und die Mitverbrennung von Abfllen - 17.
BImSchV) 17. BImSchV Ausfertigungsdatum: 23.11.1990.
Stemmler, I., Lammel, G., 2012. Long-term trends of continental-scale PCB patterns
studied using a global atmosphereocean general circulation model. Environ.
Sci. Pollut. Res. 19, 19711980.
Stockholm Convention on Persistent Organic Pollutants (Stockholm, 22 May 2001).
Technische Anleitung zur Reinhaltung der Luft nach BImSchG (TA Luft) v.
24.07.2002.
Totten, L.A., Eisenreich, S.J., Brunciak, P.A., 2002. Evidence for destruction of PCBs by
the OH radical in urban atmospheres. Chemosphere 47, 735746.
van den Berg, M., Birnbaum, L.S., Bosveld, A.T., Brunstrom, B., Cook, P., Feely, M.,
Giesy, J.P., Hanberg, A., Hasegawa, R., Kennedy, S.W., Larsen, J.C., van Leeuwen,
F.X., Liem, A.K., Nolt, C., Peterson, R.E., Poellinger, L., Safe, S., Schrenk, D., Tillitt,
D., Tysklind, M., Younes, M., Waern, F., Zacharewski, T., 1998. Toxic equivalence
factors (TEFs) for PCBs, PCDDs, PCDFs for human and wildlife. Environ. Health
Perspect. 106, 775792.
van den Berg, M., Birnbaum, L.S., Denison, M., De Vito, M., Farland, W., Feeley, M.,
Fiedler, H., Hakansson, H., Hanberg, A., Haws, L., Rose, M., Safe, S., Schrenk, D.,
Tohyama, C., Tritscher, A., Tuomisto, J., Tysklind, M., Walker, N., Peterson, R.E.,
2006. The 2005 World Health Organization re-evaluation of human and
mammalian toxic equivalency factors for dioxins and dioxin-like compounds.
Toxicol. Sci. 93, 223241.
VDI 2090-1 (01.2001) Ambient air measurement deposition measurement of low
volatile organic compounds determination of PCDD/F deposition, Bergerhoff
sampling device and GC/HRMS analysis.
VDI 3498-1 (07.2002) Ambient air measurement indoor air measurement
measurement of polychlorinated dibenzo-p-dioxins and dibenzofurans
method using large lters.
Venier, M., Hites, R.A., 2010. Time trend analysis of atmospheric POPs
concentrations in the Great Lakes region since 1990. Environ. Sci. Technol. 44,
80508055.
Venier, M., Hung, H., Tych, W., Hites, R.A., 2012. Temporal trends of persistent
organic pollutants: a comparison of different time series models. Environ. Sci.
Technol. 46, 39283934.
Verbot des Inverkehrbringens von PCB in offenen Systemen in Deutschland, Zehnte
Durchfhrungsverordnung zum Bundes-Immissionsschutzgesetz, 1978.
Verordnung zum Verbot von polychlorierten Biphenylen, polychlorierten
Terphenylen und zur Beschrnkung von Vinylchlorid (PCB-, PCT-, VCVerbotsverordnung) vom 18.Juli 1989.
Wong, F., Bidleman, T., 2011. Aging of organochlorine pesticides and
polychlorinated biphenyls in muck soil: volatilization, bioaccessibility and
degradation. Environ. Sci. Technol. 45, 958963.
Zetzsch C., 1982. Predicting the rate of OH-addition to aromatics using d
i electrophilic substituent constants for mono- and polysubstituted benzene.
In: Abstr. 15th Informal Conf. on Photochem., Stanford, California, 27 June1
July.