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DISSOLVED ORGANOCHLORINE AND PAH POLLUTION
PROFILES IN LITHUANIAN AND SWEDISH WATERAudrone
Zaliauskiene, Ilona Jegorova, Per-Anders
BergqvistEnvironmental Engineering, Kaunas
University of Technology, Kaunas, Lithuania
Environmental Chemistry, Umeå University, SE-901
87 Umeå, Sweden
Umeå
Kaunas
Introduction The purpose of this work was to
carry out a single three week monitoring in
Lithuanian and Swedish water using semipermeable
membrane devices (SPMDs) in order to estimate and
compare PCB, PAH and pesticide concentrations.
The results show, that the Lithuanian rivers
Neris and Nemunas in general are more polluted
than Swedish streams Tvärån and Djupbäcken even
comparing with Umeå river the levels was
elevated. When comparing the two Lithuanian
rivers, we found that Nemunas contains higher
concentrations than Neris. Neris and Nemunas
surrounds the Kaunas city. The sampling sites
were located downstream industrial areas and
upstream urbanized areas. The Swedish streams
were examined since no fish spawning was observed
during the last years. Large part of these
streams consist of storm water.
Results and discussion PAH From graphs below we
can see that PAH concentrations in the Swedish
streams is rather small compared with the two
investigated Lithuanian rivers. Nearly all PAH
compounds analyzed was detected in Lithuanian
rivers. Phenantrene showed the highest
concentration 7,7 ng/L. It was also found
elevated concentrations of fluoranthene and
pyrene 5,2 ng/L and 3,2 ng/L, respectively.In
the Lithuanian rivers four rings PAH compounds
dominates, and in Swedish streams dominated two
and three ring compounds. PCB Usually
concentration of PCBs decrease going from PCB 28
to PCB 180, but looking on the profile of
concentrations in Neris and Nemunas we could see
the dominating peaks for PCB 110 and PCB 118.
Since the concentrations of PCB 28 was found to
be relatively higher, it indicates that the
pollution could be more recent. PCB congeneres
were detected at higher concentrations in the
Lithuanian rivers. In Swedish waters PCB
congeners were detected only at Krokvagen and
Millbridge (PCB 28, PCB 31, PCB 44, PCB 110),
and these concentrations were close to detection
limit. The highest concentrations in Lithuanian
rivers were observed for PCB 28 0,43 ng/L, PCB
31 0,24 ng/L, PCB 110 0,33 ng/L.
PAH concentrations in sampling places
PCB concentrations in sampling places
Materials and methods Semipermeable membrane
devices (SPMDs) are passive samplers used for
measuring the truly dissolved concentration of
Persistent Organic Pollutant (POPs) in water.
SPMD devices are new, versatile, non-destructive
methods, without any advanced or costly equipment
requirements. Semipermeable membranes filled with
lipophilic solvent are possible to use for the
evaluation of bioavailability of organic
compounds. SPMD data can be used to study
variation in organic pollutant concentrations in
space and time. As an alternative high volume
sampling, semipermeable membrane devices (SPMDs)
in water, was performed during 21 days. 6
sampling places was choosen for investigation.
Pesticides The pesticide concentrations in the
samples displayed higher concentrations in the
Lithuanian rivers. Only o,p-DDE (2,1 ng/L), ?-HCH
(0,54 ng/L) and p,p-DDE (0,66 ng/L) at the
Upstream sampling site was higher in the Swedish
streams investigated. Before the sampling site
Upstream agricultural land, forests and green
houses were dominating and could be the reason of
pesticides leaking to stream. The highest
concentrations in Lithuanian rivers were of the
DDT metabolite DDMu 1,17 ng/L, o,p-DDE 1,57
ng/L, p,p-DDD 0,41 ng/L. Pollution
comparison In the last graph a comparison
between the large rivers in Lithuania and one
large river in Sweden can be seen indicating that
the concentration of sumPAH in Neris and Nemunas
was also elevated compared to Umea river. Higher
concentrations were also identified for sumDDT
and sumPCB. The dissolved water concentrations of
?-HCH (purified HCH products which consist of at
least 99 ?-isomers are marketed under the
comercial name lindane.), hexa-CBz and sumCHL
(chlordane, which consist of a mixture of more
than 140 different components) were similar in
all three river sites.
PLACE EXPOSURE SITE
1 UPSTREAM upstream industrial area
2 KROKVÄGEN downstream industrial area
3 MILBRIDGE downstream before Umeå river
4 HOSPITAL different type of storm water
5 NERIS Lithuanian river (upstream industrial area)
6 NEMUNAS Lithuanian river (downstream industrial area)
The compounds were dialysed and then fractionated
by gel permeation chromatography (GPC) technique
followed by a silica column. PAHs, PCBs and
pesticides were identified by gas chromatography
and mass spectrometry (GC/MS). Interpretation of
chromatograms and calculation of concentrations
was done using sixteen internal standard
(IS). SPMD technology are used to estimate
ambient TWA (time weighted average) dissolved or
vapour phase chemical concentrations.
Pesticide concentrations at sampling sites
Comparison of pollution in three rivers
SIM In these figures we can see selected ion
monitoring (SIM) chromatograms of five homolog
groups of PCB from the Lithuanian river Nemunas
at Kaunas and from sampling site Krokvägen in
Tvärån stream in Umea, Sweden. For hexa-PCB (6
chlorine atoms in the chlorinated biphenyl) only
limited amounts are dissolved in water. From
the figures we can see, that Nemunas is more
polluted than Tvärån stream. At sampling site
Krokvägen an un-known compounds were detected at
high concentration at 18,58 min reducing the
visibility of di-PCB (2 chlorine atoms), but this
homolog group is visible in Nemunas sample.
Tri-PCB (3 chlorine atoms) pattern is not seen
because of the large un-known peak with retention
time 14,44 min. Tetra-PCB (4 chlorine atoms) was
easily identitied in both places. Penta-PCB (5
chlorine atoms) was very close to detection limit
in Sweden. SPMD sampling results in clean
extract which is easy to evaluate, and the
clean-up procedure can include only
non-destructive steps.
PCB from site Nemunas and from site Krokvägen

• Conclusions
• Using SPMD it is possible to compare sampling
  sites in different places and countries at the
  same time
• data from Integrated sampling of bioavaible
  compounds during 21 days was evaluated
• Lithuanian rivers were generally more polluted
  than Umeå streams and Umeå river.
• PAH concentrations were ten times higher in
  Lithuanian rivers than in Umeå river
• PCB concentrations were also higher in
  Lithuanian rivers. In Umeå streams PCB
  concentrations were equal
• the relatively higher concentration of low
  molecular weight PCB (as PCB28) indicates a
  recent pollution in Lithuania
• DDT and lindane were detected before industrial
  area in Umeå (in upstream site). DDT
  concentrations were higher in Nemunas than in
  Neris

Acknowledgements We wish to acknowledge Umea
University, Socrates program and Kaunas
University of Technology for financial support.