Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland).
ABSTRACT Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.
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ABSTRACT: Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in surface sediment samples from Taihu Lake--an important water supply of the Yangtze River Delta, China--were investigated in the present study. Concentrations of PCDD/Fs ranged from 0.91 to 4.8 pg TEQ g(-1) dw (mean: 2.9 pg TEQ g(-1) dw, TEQ: Toxic Equivalent), which were all higher than the threshold effect level established by interim sediment quality guidelines in Canada (0.85 pg TEQ g(-1) dw). The levels of PBDD/Fs ranged from 0.16 to 1.6 pg TEQ g(-1) dw (mean: 0.52 pg TEQ g(-1) dw) and accounted for 5-33% (mean: 14%) of the total PCDD/Fs and PBDD/Fs TEQ. Comparatively, the abundance of sedimentary PCDD/Fs in the three regions (Meiliang Bay, Gonghu Bay, and Xukou Bay) showed a decreasing trend from the inflow region to the outflow region, while no significant difference was observed among their 2,3,7,8-PBDD/Fs levels, which suggested that the sources of PCDD/Fs and PBDD/Fs differed in this area. Principal component analysis suggested that the historical production/usage of pentachlorophenol and sodium pentachlorophenate was the dominant source of PCDD/Fs in the sediment of these regions. Although the specific sources of PBDD/Fs in the sediment of Taihu Lake were unclear, it was suspected to be due to atmospheric deposition; however, an additional study is needed to confirm this.Journal of Environmental Monitoring 05/2012; 14(7):1935-42. · 2.09 Impact Factor
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ABSTRACT: The development of a unique analytical method for the determination of five classes of persistent organic pollutants (POPs) in atmospheric gas and the particle phase through gas chromatography coupled to high-resolution mass spectrometry is presented. Every step of the pre-analytical and analytical optimization process is described. Great effort was put into simplifying the traditional techniques, with reference to EPA and literature methods. Automated instruments were used for sample extraction and cleanup in order to enhance repeatability and reduce contamination risks. Unlike most common approaches, no separation of the analytes was performed before the GC analysis in order to avoid sample fractionation and to save time and materials. This allowed low instrumental and method detection limits (pg to sub-pg) to be achieved. Accuracy and precision were tested by fortifying the matrix and analysing standard reference materials (NIST SRM 1649b Urban Dust and 2585 Organic Contaminants in House Dust). The method was applied to five samples from Terra Nova Bay, Antarctica. Concentrations of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) are presented. Lighter compounds dominate the distribution and are mainly present in the gaseous phase. The observed pattern may be attributable to long-range transport. Results are in general agreement with literature data, where available.Analytical and Bioanalytical Chemistry 10/2012; · 3.66 Impact Factor
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ABSTRACT: 24 surface sediment samples were collected from the Bering Sea, Chukchi Sea, and Canada Basin during the 3rd Chinese National Arctic Research Expedition in July–September 2008. To obtain information on the levels, spatial distribution, possible sources, and influences of total carbon and black carbon, we analyzed the samples for polybrominated diphenyl ethers (PBDEs) and decabromodiphenylethane (DBDPE). Concentrations of P PBDEs (hereafter, P PBDEs refers to the sum of all detected PBDE congeners without BDE-209), BDE-209, and DBDPE were in the ranges 3.58–148.95 pg/g d.w. (dry weight), n.d. À 804.91 pg/g d.w. and n.d. À 452.57 pg/g d.w., respectively. The congener patterns of PBDEs suggested that BDE-209 was the major congener in these areas, followed by BDE-99 and À 47, which was consistent with the predominance of technical deca-BDE mixtures in the dominant technical PBDE mixtures. The significant relationships of BDE-209, -47, and -99 and total PBDEs with total organic carbon and black carbon, as well as the skewed distribution of P PBDEs and BDE-209, indicated that atmospheric deposition and local discharge might be potential sources in this area, and the distribution pattern may be the combined effect of multiple factors.· 2.24 Impact Factor
Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans
(PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated
diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland)w
Ingrid Vives,*aElisabetta Canuti,aJavier Castro-Jime ´ nez,aEugen H. Christoph,a
Steven J. Eisenreich,bGeorg Hanke,aTania Huber,aGiulio Mariani,a
Anne Mueller,aHelle Skejo,aGunther Umlaufaand Jan Wollgasta
Received 23rd January 2007, Accepted 12th March 2007
First published as an Advance Article on the web 11th April 2007
Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and
sediments were collected in Lake Maggiore (LM) in order to determine their content of
polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls
(PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases)
concentrations were 0.5 pg m?3, 80 pg m?3, 13 pg m?3and 106 pg m?3for SPCDD/Fs, SPCBs,
S dioxin-like PCBs (DL-PCBs) and SPBDEs, respectively. Deposition fluxes ranged from 0.7 ng
m?2d?1for SPCDD/Fs to 32 ng m?2d?1for SPCBs. Aquatic settling material presented
concentrations of 0.4 ng g?1dry weight (dw) for SPCDD/Fs, 13 ng g?1dw for SPCB, 3.4 ng g?1
dw for SDL-PCBs and 5.7 ng g?1dw for SPBDEs. Mean sediment concentrations were 0.4 ng
g?1dw for SPCDD/Fs, 11 ng g?1dw for SPCB, 3 ng g?1dw for SDL-PCBs and 5.1 ng g?1dw
for SPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental
compartments of LM point to an important, if not dominant, contribution of atmospheric
deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was
not similar in the different environmental compartments. BDE 47 dominated air and settling
material, while BDE 209 was the predominant congener in the bulk atmospheric deposition.
Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated
sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE
concentrated samples. This suggests the influence of local sources as well as atmospheric input of
PBDEs into LM.
Anthropogenic contaminants are loaded into aquatic systems
through point and diffuse sources. Depending on their physi-
co-chemical properties, their use and transport processes,
chemical distribution may be widespread or local. Aquatic
sediments are a sink for hydrophobic organic contaminants
and may pose an unacceptable risk to aquatic organisms.
(PCDD/Fs), polychlorinated biphenyls (PCBs) and polybro-
minated diphenyl ethers (PBDEs) are persistent organic
pollutants which enter the environment as a result of anthro-
pogenic activities. These compounds, emitted into the
atmosphere, can be transported over long distances.1After
deposition they are distributed into various environmental
compartments. Many congeners bioaccumulate and are con-
sidered potent toxicants, capable of producing a wide spec-
trum of adverse health effects in biota and humans, such as
carcinogenicity, reproductive and developmental toxicity, dis-
ruption of the endocrine system, induction of enzymes, estro-
genic and anti-estrogenic effects.2–5These group of chemicals
are present in complex mixtures in the environment.
PCDD/Fs are formed as unintentional byproducts of che-
mical manufacturing and incineration processes.6,7Emissions
from incineration of industrial wastes such as metal reclama-
tion and domestic heating (especially in central Europe) are
considered as current sources of PCDD/Fs to the environ-
ment.8,9Among the 210 different PCDD/F congeners, only
those isomers presenting chlorine substitution in the 2,3,7,8
positions have been reported to present toxic properties.10
PCBs were mainly used by the power industry in electrical
transformers, capacitors, hydraulic equipment, and as lubri-
cants. These compounds were also added to many consumer
products, like adhesives, waxes and inks. Since the mid 1970s
PCBs have been banned from active use in most countries due
to their toxicity and extreme persistence. However, sediments
of rivers, lakes, and oceans, and soils of temperate areas, as
well as marine waters are primary locations for PCB
aEuropean Commission—DG Joint Research Centre, Institute for
Environment and Sustainability, Via E. Fermi 1, 21020 Ispra (Va),
Italy. E-mail: firstname.lastname@example.org; Fax: +39 0332 786351;
Tel: +39 0332 786639
bEuropean Commission—DG Joint Research Centre, Institute for
Health and Consumer Protection, European Chemicals Bureau,
Via E. Fermi 1, 21020 Ispra (Va), Italy
w Presented at Sources, Fate, Behaviour and Effects of Organic
Chemicals at the Regional and Global Scale, 24th–26th October
2006, Lancaster, UK.
This journal is ? c The Royal Society of Chemistry 2007J. Environ. Monit., 2007, 9, 589–598 | 589
PAPERwww.rsc.org/jem | Journal of Environmental Monitoring
accumulation in the environment and, therefore, themselves
can act as emission sources if environmental conditions
Twelve out of the 209 existing PCB congeners have been
identified as dioxin-like PCBs (DL-PCBs) by the World Health
Organization (WHO).10Their molecular characteristics make
them similarto the2,3,7,8-tetrachlorodibenzo-p-dioxin
(2,3,7,8-TCDD), since they can adopt a co-planar confi-
guration, and they exhibit toxicity in a manner similar to
PBDEs constitute an important group of brominated flame
retardants and, unlike PCBs, are still being used as additives in
commercial products (especially in electrical equipment and
textiles) to meet fire safety regulations. Three major PBDE
commercialmixtures are commonly
Deca-BDE, Octa-BDE and Penta-BDE. Their usage in Eur-
ope during 2001 was 7600, 610, and 150 tons, respectively.15
According to the EU Risk Assessment,16,17the Penta- and
Octa-BDE formulations are banned since August 2004,18
while the Deca commercial product received an exemption
to the ban, and this exemption is presently under evaluation.
Temporal trends have shown recent PBDE concentrations to
increase in sediment and biota tissues.19–22The occurence of
these compounds in the environment has also been reported in
remote sites, where the atmosphere is the only pollutant input
and global distribution of PBDEs deserve growing concern
because of their stability, lipophilicity and potential bioaccu-
mulation and toxicity.22,26,27
PCDD/Fs, PCBs and PBDEs are delivered to lake systems
by atmospheric deposition, air–water interchange, direct dis-
charges and riverine inputs. These compounds are character-
ized by low aqueous solubilities, medium vapour pressures,
and resistance to extensive physical, chemical and biological
transformation. Their general hydrophobic nature results in
high partition coefficients to organic matter, to biotic tissues
and to black carbon delivered into the lake system.
PCDD/Fs, PCBs and PBDEs exist in the atmosphere as
gases and bound to particles. Most measurements are domi-
nated by the aerosol concentrations for PCDD/Fs, whereas
total airborne PCBs are normally dominated by the gas-phase
burden.28,29Most of the PBDEs are evenly distributed
between gas and particle phases.30,31
Once delivered to the water column, the primary removal
processes are sedimentation of atmospheric particles and
partitioning of the gaseous/dissolved phase contaminants into
organic carbon (OC)-rich particles with subsequent settling,
and finally accumulation in surface sediments. The final con-
taminant and particle burial is slowed by the effects of
resuspension of sediments and bioaccumulation in aquatic
The present study was conducted in Lake Maggiore (LM)
situated at the south of the Alps, northwest of the industria-
lized area of Milan, Italy (Fig. 1). The lake is located at 194 m
above sea level and is the second largest (212.5 km2) and the
deepest (370 m) of the Italian lakes. Input from the catchment
area (6600 km2) into the lake occurs directly and through three
major rivers and numerous smaller creeks. The Ticino River is
the only outflow from LM. Besides a recreational use of its
15,20,22–25The widespread environmental presence
waters (swimming, diving and yachting), the lake is used as
source of water for the population in the area, fisheries and
Several studies carried out in LM have provided insight into
the pollution levels of the lake: mercury contamination from
mining and other industrial activities, eutrophication, and
more recently a large DDT discharge into the lake. DDTs,
hexachlorocyclohexanes, hexachlorobenzene and PCB con-
centrations have been determined in water, sediments and
biota from the lake.32–35
Concentrations of polycyclic
aromatic hydrocarbons in surface water and precipitation
input to the lake have been recently reported.36However,
only few data on environmental concentrations and fate of
PCDD/Fs, DL-PCBs and PBDEs in this aquatic system are
available to date.37–40
The aim of the present study is to expand the existing
database on persistent organic pollutants in the different
environmental compartments of LM and to elucidate the role
of the atmosphere as an important source of pollutants into
the lake. To achieve our goals, air (gas and particulate phases),
bulk deposition, aquatic settling material, and sediment sam-
ples were collected and analysed for 17 toxic PCDD/F,
18 PCB and 8 PBDE congeners.
Sample location details are depicted in Fig. 1.
Air and bulk deposition. A high volume air sample and bulk
deposition sample were collected simultaneously from March
22nd to March 30th 2005 at the Joint Research Centre (JRC)
EMEP site (Cooperative Program for Monitoring and Eva-
luation of the Long-Range Transmission of Air Pollutants in
Europe) at Ispra, Italy. Meteorological conditions of this
period were characterised by minimum and maximum tem-
perature ranges of 6–10 1C and 12–25 1C, respectively, an
average wind speed of 7 m s?1and a bulk precipitation of
108 mm. Meteorological data were obtained from the
European Solar Test Installation site at JRC.
Air samples were collected with a high volume sampling
device (Echo PUF Hi Volume Sampler, TCR Tecora, Milan,
Italy) equipped with a pre-cleaned glass fiber filter (GFF)
(102 mm diameter) and a pre-cleaned polyurethane foam
(PUF) (65 mm diameter) for sampling particulate and gas
phases, respectively. A sample of 845 m3was collected and
both phases were separately analysed.
A validated rain collector holding three glass funnels of
188 mm diameter each was used for the precipitation collec-
tion. A PUF plug of 18 mm diameter and 100 mm length was
placed in each neck funnel.41Precipitation intensity was
estimated by gravimetry. During the sampling period E3 L
of bulk precipitation were collected.
Aquatic settling material. Aquatic settling matter was col-
lected with a sediment trap at a depth of 27 m and 3 m above
the lake sediment, covering a period of 4 months, from
December 2004 to April 2005. The sediment trap was deployed
at Quassa Bay (southern part of LM) at a distance of 400 m
590 | J. Environ. Monit., 2007, 9, 589–598This journal is ? c The Royal Society of Chemistry 2007
from the coast and about 2.5 km from the atmospheric
sampling site. This location is a sedimentation zone with no
direct inputs from local tributaries.
The sediment trap was a stainless steel cylinder (50 cm
diameter and 150 cm length with funnel end) that leads into
a 250 mL glass vessel equipped with an acoustic release unit
7986 LRT (Sonardyne, Yateley, UK). The collected sample
(16 g) was centrifuged, decanted, frozen, freeze dried and
stored in dark bottles in a cool place until analysis. An amount
of 5 g was processed.
Sediment. Forty-eight superficial sediment samples were
collected at depths between 5 and 60 m in LM during 2005.
The sediment sampling sites were homogeneously distributed
along the extension of the lake, including sites near river inlets/
outlets and sites located in settling basins (Fig. 1).
Sediment samples were collected using a Ponar Grab Sam-
pler from a boat. The sampled sediment depth was around 10
cm. Supernatant was decanted and sediments were frozen and
freeze dried (Lio5P, 5 Pascal, Trezzano, Italy). Material
42 mm was removed by sieving. Sediment samples were then
stored in dark bottles in a cool place until analysis. Each
processed sample consisted of about 30 g dry weight (dw).
Sigma–Aldrich (Buchs SG, Switzerland). All the gases (Alpha-
gaz, Italy) used were ultrapure grade suitable for PCDD/F
analysis. Sulfuric acid 98% extra pure was obtained from
VWR International s.r.l. (Milan, Italy). Pre-packed multi-layer
silica, basic alumina and carbon columns were purchased from
Fluid Management Systems Inc. (Watertown, MA, USA).
Glass fiber extraction thimbles (MN649) werepurchased from
Macherey-Nagel (Du ¨ ren, Germany) and copper powder (?200
mesh, 99%) was from Sigma–Aldrich (Steinheim, Germany).
(Wellington Laboratories, Guelph, Ontario, Canada) were
native,13C-labelled internal and injection standards, respec-
tively, for 17 PCDD/F congeners.
13C-labelled PCB standards (EC 4058) were obtained from
CIL (Andover, MA, USA). Standard mixtures 68-CVS and
68-LCS (Wellington Laboratories, Guelph, Ontario, Canada)
were native and
DL-PCB congeners, respectively.
Penta/octa/deca-bromo standard solutions were obtained
from Dr Ehrenstorfer GmbH (Augsburg, Germany).
labelled standards (according to IUPAC nomenclature:
BDE-28, BDE-47, BDE-99, BDE-100, BDE-118, BDE-153,
BDE-183) were obtained from CIL (Andover, MA, USA).
13C-labelled internal standards for 12
Sample extraction and cleanup
A sample preparation method for determination of PCDD/Fs
and PCBs was adopted to include PBDEs in the analysis of the
Fig. 1 Location of Lake Maggiore and sampling sites.
This journal is ? c The Royal Society of Chemistry 2007J. Environ. Monit., 2007, 9, 589–598 | 591
extract of different matrices. Samples were extracted with a
mixture of n-hexane–acetone (220 : 30; v/v) by Soxhlet for 24 h
after being spiked with
(16 congeners of 2,3,7,8-PCDD/F, 7 congeners of PCBs, 12
congeners of dioxin-like PCBs and 7 congeners of PBDEs).
For sediments and settling material, copper powder was added
to the solvent during the extraction to remove sulfur. Extracts
were evaporated to nearly dryness and refilled to 10 mL with
Sediment and settling material extracts were treated with
concentrated H2SO4prior the following purification step. This
oxidative process provides a good procedure to eliminate
many organic components that could interfere in the analyses
Cleanup of the extracts was executed with an automated
system (Power Prep P6, from Fluid Management Systems
(FMS) Inc., Watertown, MA, USA). This system, previously
described by Abad et al.,42uses a multi-layer silica column, a
basic alumina column and a carbon column combination. Two
fractions were collected, one containing indicator PCBs and
PBDEs and one for PCDD/Fs and DL-PCBs.
Purified extracts were evaporated to nearly dryness under a
gently nitrogen flow (Turbovap, Zymark, USA) and filled up
with 30 mL of toluene.
Prior to injection,
determine the recoveries of the internal standards.
13C-labelled internal standards
13C-labelled standards were added to
Instrumental analysis of PCDD/Fs, PCBs and PBDEs was
carried out using a high resolution gas chromatograph
(HP-6890, Hewlett Packard/Agilent, Waldbronn, Germany)
coupled with a VG Autospec Ultima high resolution mass
HRMS). The operating mode was electron impact at 34 eV
with a resolution of 410000. Split/splitless injector was set at
Non-ortho PCBs and PCDD/Fs were analyzed on a BP-
DXN capillary column, whereas for the mono-ortho PCBs an
HT-8 capillary column was used. Both columns were 60 m
long, 0.25 mm i.d. (inner diameter) and 0.25 mm film thickness.
PBDEs were analyzed on a Sol-Gel-1 MS capillary column,
15 m long with 0.25 mm i.d. and 0.1 mm film thickness. All
capillary columns were obtained from SGE, Victoria, Australia.
For PCDD/F and PCB congeners and the corresponding
labelled standards two ions each were registered. For tri- to
octa-brominated congeners, two ions of the isotopic molecular
cluster were recorded both for native and labelled congeners.
For nona- and deca-brominated congeners two isotopic ions
of the cluster M+–2Br were recorded for native compounds.
The identification was done by retention time comparison
of the corresponding internal standard and isotopic ratio
between two ions recorded. When standards were not avail-
able, identification was optimised following literature indica-
Quantification was done by the isotope dilution method
following the EPA1613, EPA1614 and EPA1668 protocols,
except for deca-BDE where the internal standard13C-BDE-183
Levels are reported as SPCDD/Fs, SPCBs, SDL-PCBs and
SPBDEs. The PCDD/Fs analysed were all the 2,3,7,8-chlorine
substituted congeners. SPCB includes the indicator PCB con-
geners with IUPAC numbers 52, 101, 118, 138, 153, and 180.
SDL-PCBs included four non-ortho PCBs (congeners 81, 77,
126, and 169) and eight mono-ortho PCBs (congeners 105, 114,
118, 123, 156, 157, 167, and 189). These congeners comprise
the so-called dioxin-like PCBs as described by the WHO.
PBDEs analysed included congeners 28, 47, 100, 99, 154,
153, 183, and 209.
Total organic carbon analysis
The content of total organic carbon (TOC) of sediments was
analyzed using a TOC-5000A instrument (Shimadzu, Europe
GmbH) according to the ISO10694 method.
Quality assurance and quality control were done by carrying
out simultaneously laboratory blanks together with each batch
of 15 samples. Only concentration values at least 10 times
higher than the blank values were considered in the present
The detection limits were calculated directly on the samples
taking into consideration a signal/noise ratio of 3/1. Recov-
eries of the13C-labelled compounds in all cases ranged from 50
to 100%, which falls within the limits established by the EPA
In addition, the analytical methodologies employed were
tested by the parallel analysis of a sediment sample from the
9th International Intercalibration Study47for PCDD/Fs and
PCBs. No environmental matrix was available as reference
material for PBDE analysis.
Results and discussion
The pollutant levels in air (gas and particulate phases), deposi-
tion, settling material and sediments of LM are summarised in
Table 1 and the chemical groups are separately discussed
The SPCDD/F (gas and particulate phases) concentrations in
air and bulk deposition near LM were 532 fg m?3and 760 pg
m?2d?1, respectively (Table 1). These values are in agreement
with levels reported for rural sites.48–52SPCDD/F concentra-
tions in the particulate phase were one order of magnitude
higher than in the gas phase. Bulk deposition flux is approxi-
mately one order of magnitude less than what has been found
in polluted sites in Japan.53
PCDD/Fs were found in all sediment samples (n = 48),
including those under direct influence of riverine inputs.
SPCDD/F sediment concentrations ranged from 3.5 pg g?1
dw to 2211 pg g?1dw (0.1–32 pg WHO TEQ g?1dw), with a
mean value of 435 pg g?1dw (Table 1). Settling mat-
erial presented a similar PCDD/F concentration value
(490 pg g?1dw).
SPCDD/F sediment concentrations in the present study are
in the range of those considered to be background levels due to
atmospheric deposition.54–56Suspended particulate matter
592 | J. Environ. Monit., 2007, 9, 589–598This journal is ? c The Royal Society of Chemistry 2007
from up-stream of Trenton Chanel in Detroit River (non-
impacted zone) presented similar values.57
The spatial distribution of SPCDD/Fs in LM shows that
sediments located in the northern basin(s) exhibit significantly
lower concentrations than the ones from the central and
southern basins (p o 0.001). Mean SPCDD/F values from
the north (n = 11), central (n = 23) and south (n = 14)
sediments are 64 pg g?1dw, 489 pg g?1dw and 648 pg g?1dw,
respectively. The north–south gradient could be caused from
the flushing of the sediment from the north to the south due to
intermittent re-suspension in the shallower north basin and the
natural north–south direction of lake water flow, as well as
input locally only to the southern basin.
When PCDD/F concentrations are normalized to TOC
content, the spatial variation between samples decreases from
a factor of 246 (dw basis) to a factor of 85 (OC weight basis).
This observation is supported by the plot of SPCDD/F
concentrations versus sedimentary TOC (Fig. 2). Sediments
from flushing regions (near riverine inlets and outlets) of the
lake show a linear relationship between concentration and
TOC, while the settling basin sediments show a logarithmic
relationship. Moreover, settling basin sediments present sig-
nificantly higher TOC normalized PCDD/F concentrations
than the ones found in flushing sediment regions (p o 0.001).
These findings suggest that in the settling basins, where
organic matter is continuously settling, decomposition of
organic matter leads to a reduction of OC, and therefore a
higher PCDD/F load per unit of TOC.
Fig. 3 shows the PCDD/F congener profile distribution in
the LM basin. Throughout the basin, congener profiles are
remarkably similar, dominated by octachloro- and hepta-
chloro-dioxins, followed by octachloro- and heptachloro-
furans. This sedimentary pattern is attributed to long range
atmospheric transport.48,55,56At all but two sites, a single
congener (OCDD) accounted for more than 40% of the total
PCDD/Fs. The sediment sample taken at the inlet of River
Bardello (Fig. 1) differed from the general pattern, and the
distribution was dominated by octachlorodibenzofuran fol-
lowed by octachlorodibenzodioxin. The predominance of the
cited PCDD/F congeners has been related to industrial pro-
cesses, such as oxychlorination or ethylene dichloride produc-
tion56,58and metal industry.59However, in the present study,
the PCDD/F source for the Bardello sediment signal could not
The spatial homogeneity of the PCDD/F sediment pattern
along the whole lake underlines the absence of important local
sources and riverine inputs into LM. Moreover, the sediment
pattern is similar to that of PCDD/Fs in atmospheric parti-
culate matter and bulk deposition (Table 2), which, as stated
before, represents a typical profile for long range atmospheric
transport. Mass balance fluxes of PCDD/Fs into LM as well
as congener patterns in the different compartments of the lake
presented elsewhere60suggest that atmospheric deposition is
Table 1Levels of PCDD/Fs, PCBs and PBDEs in air, bulk deposition, settling material and sediments in Lake Maggiore
Air gas phase
22–30 Mar 05
Air particle phase
22–30 Mar 05
22–30 Mar 05
17 Dec 04–19 Apr 05
/ng g?1dry weight
/ng g?1dry weight
0.34 (n = 48)
0.095 (n = 48)
11 (n = 22)
3.0 (n =22)
5.1 (n = 8)
aAll 2,3,7,8 substituted congeners.b52,101,118,138,153 and 180 congeners.cNon-ortho (81, 77, 126, 169) and mono-ortho (105, 114, 118, 123,
156, 157, 167, 189) congeners.d28, 47, 100, 99, 154, 153, 183 and 209 congeners.
equivalent) vs. total organic carbon of the sediment.
PCDD/F concentration (expressed in pg g?1WHO-total toxic
(average % ? SD) (n = 48).
PCDD/F congener pattern in the Lake Maggiore sediments
This journal is ? c The Royal Society of Chemistry 2007J. Environ. Monit., 2007, 9, 589–598 | 593
the dominant input mode for the introduction of PCDD/Fs
into LM sediments.
Indicator PCBs. Air (gas and particulate phases) shows a
SPCB concentration of 80 pg m?3(Table 1). This value is
similar to those reported for rural and remote sites from
around the world.28,61–68More than 90% of all PCBs analysed
in air were found in the gas phase, in agreement with previous
Bulk deposition showed a SPCB flux of 32 ng m?2d?1
(Table 1). This value is in the range of what has been found in
European and North American rural and urban sites (3.8–
20 ng m?2d?1).69–71However, remote sites and the open
oceans present SPCB deposition concentrations at least one
order of magnitude less than in LM.72,73
SPCB settling material concentration was of 13 ng g?1dw
(Table 1). This value is within the range found in a study on
the River Guadiana in Portugal that reported concentrations
between 0.4 ng g?1dw and 30 ng g?1dw for suspended
Sediments exhibit SPCB concentrations between 0.3 ng g?1
dw and 38 ng g?1dw, with a mean value of 11 ng g?1dw (n =
22) (Table 1). These values are in agreement with values
reported in another study on LM.75Sediments from River
Guadina (Portugal) and Niagara River (USA) show SPCB
concentrations of 0.1–1.8 ng g?1dw and 1.7–124 ng g?1
dw,74,76respectively. Rural and remote lake sediments present
lower range of SPCB concentrations (0.05–2.5 ng g?1dw in
Finland and 2.3–15 ng g?1dw in European high mountain
PCB congener pattern varied among the different environ-
mental compartments of LM (Table 2 and Fig. 4). PCB 52
dominated the atmospheric gas phase and deposition profiles
(around 30% of the total PCBs). This is in agreement with
results presented for other rural areas.65
Higher chlorinated PCBs (congeners 138 and 153) were
predominant in the settling material and sediments (each
around 20% of SPCB) (Table 2 and Fig. 4). The predomi-
nance of congeners 138 and 153 in sediments has been widely
found in other freshwater ecosystems.76,77Congener 153 was
also the most abundant in the LM sediments published else-
SDL-PCB concentration in air (gas and particulate phases)
was 13 pg m?3(Table 1). This value is nominally higher than
the levels reported for rural area in Germany.78Gas-phase
DL-PCB concentrations were higher than in the aerosol, as
observed with the other PCB congeners reported.
Table 2PCDD/Fs, PCBs, DL-PCBs and PBDEs congener patterns (%) in air, bulk deposition, settling material and sediments of Lake Maggiore
Particulate phase Bulk depositionSettling material Sediments
2,3,7,8- isomers PCDD/FsTCDD
an.d. not detected.bTwo distinct sediment patterns were found. Mean relative distribution is presented for each group.
594 | J. Environ. Monit., 2007, 9, 589–598This journal is ? c The Royal Society of Chemistry 2007
Total deposition flux of SDL-PCB was 7 ng m?2d?1
(Table 1). Similar values have been reported for an urban
area in Japan.53The settling material presented SDL-PCB
concentrations of 3.4 ng g?1dw (Table 1). This is in the range
of values considered as background level in other studies.57
SDL-PCB concentrations in surface sediments (n = 22)
ranged between 0.08 ng g?1dw and 11 ng g?1dw. Mean
DL-PCB concentration in sediment was 3 ng g?1dw (Table 1).
DL-PCB concentrations found in sediments from a lake in
China are in the lower range of those reported in the present
study,79while similar values to our results are found in coastal
sediments in Spain.56
The congener patterns were similar in all studied compart-
ments (Table 2). Among the non-ortho congeners, PCB-77 was
found at a highest concentration, whereas PCB-118 followed
by PCB-105 and PCB-156 were predominant among the
mono-ortho congeners. Similar results were reported from a
rural area in Germany,78from coastal sediments in Spain56
and from Chinese lake sediments.79
The homogeneity in DL-PCB congener pattern in all the
environmental compartments (Table 2) indicates that the
atmosphere is the dominant source of these pollutants into
LM. An estimation of DL-PCB mass balance fluxes in LM
supports these findings.60
SPBDE air (gas and particulate phases) concentration was
106 pg m?3, and 72% was in the gas phase (Table 1). Similar
PBDE concentrations values were found in air of urban sites
in Europe,80,81North America,31,82and Asia.83
Air PBDE congener pattern was dominated in both phases
by BDE 47 (Table 2). The higher contribution of congener 47
in air samples has also been found by Shen et al.67and
Stranberg et al.31in the North America atmosphere. BDE
154, 153, 183 and 209 were only detected in the particulate
phase of the air. PBDEs have been described to be distributed
between the gas and the particle phases, with lighter congeners
found in the gas phase and heavier ones in particle phase.30,31
Deposition of SPBDE was 17 ng m?2d?1(Table 1). Similar
values of PBDE deposition have been reported for rural sites
in other studies.41,84BDE 209 was the predominant congener
in the bulk deposition as it has for other studies.41,84
Settling material exhibited a SPBDE concentration of
5.7 ng g?1dw (Table 1). Only a few studies report PBDEs in
settling material in lakes. Moche and Stephan85reported 0.38
ng g?1dw and 1.1 ng g?1dw for two samples of suspended
particulate matter in the River Danube in Austria (17 BDE
congeners considered). Congeners 47 and 99 accounted for
nearly 65% of the total PBDE concentration found in settling
material (Table 2). BDE 47 and 99 concentrations in the
present work were similar to a study carried out in surface
waters in the Netherlands.86However, the mentioned study
reports higher concentrations for BDE 209 (mean of 71 ng g?1
dw) than found in LM (0.52 ng g?1dw).
Minimum and maximum SPBDE concentrations in sedi-
ments (n = 8) were 0.06 ng g?1dw to 27 ng g?1dw,
respectively. A mean concentration of SPBDE in sediments
was 5.1 ng g?1dw (Table 1). The range of BDE concentrations
is similar to what has been reported for other fresh-
Two different congener profiles were found in the set of
sediment samples (Table 2). BDE 209 was the predominant
congener in sediment samples with high concentrations of
PBDEs. However, BDE 47 and 99 were predominant in
samples with low concentrations. Congener BDE 209 consti-
tuted between 50–99% of the total PBDE concentrations in
Spanish coastal sediments, with a higher range of concentra-
tion (2.7 ng g?1dw to 134 ng g?1dw) in comparison with our
PCDD/F, PCB and PBDE content in air, bulk deposition,
settling material and sediments from Lake Maggiore was
analysed. Concentrations of these pollutants were in the range
of those reported for rural areas and other freshwater systems
with background environmental levels.
The atmospheric particulate phase PCDD/F pattern was
similar to the ones found in all the environmental compart-
ments studied in the lake. In contrast, lighter PCBs dominated
the air gas phase whereas heavier PCBs were predominant in
settling material and sediments.
Two distinct congener distribution profiles were found for
PBDEs in sediments, which may respond to the existence of
local input sources for these pollutants into LM.
Ongoing research on LM will evaluate, in more depth, the
spatial and temporal variances of these pollutants in order to
identify the existence of local sources and the annual con-
tribution of atmospheric loads.
PCB congener pattern of the deposition chain into the Lake
This journal is ? c The Royal Society of Chemistry 2007J. Environ. Monit., 2007, 9, 589–598 | 595
We thank Wolfgang Mehl and Friedrich Lagler for the help
with the recovery of the sediment trap and Alessandro
Dell’Acqua for the collaboration regarding the EMEP Station.
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598 | J. Environ. Monit., 2007, 9, 589–598 This journal is ? c The Royal Society of Chemistry 2007