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Bulk deposition of PAHs, PCBs andHCHs in Finland in summer seasons1993–1996M. Korhonen a , A. Kiviranta b & R. Ketola ba Impacts Research Division , Finnish Environment Institute ,P.O. Box 140, Helsinki, FIN‐00251, Finlandb Technical Research Centre of Finland , ChemicalTechnology , P.O. Box 1401, F1N‐02044 VTT, FinlandPublished online: 19 Sep 2008.

To cite this article: M. Korhonen , A. Kiviranta & R. Ketola (1998) Bulk deposition of PAHs, PCBsand HCHs in Finland in summer seasons 1993–1996, Toxicological & Environmental Chemistry,66:1-4, 37-45, DOI: 10.1080/02772249809358581

To link to this article: http://dx.doi.org/10.1080/02772249809358581

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Toxicological and Environmental Chemistry, Vol. 66, pp. 37-45 © 1998 OPA (Overseas Publishers Association)Reprints available directly from the publisher Amsterdam B.V. Published under licensePhotocopying permitted by license only under the Gordon and Breach Science

Publishers imprint.Printed in India.

BULK DEPOSITION OF PAHs, PCBs AND HCHsIN FINLAND IN SUMMER SEASONS 1993-1996

M. KORHONENa,*, A. KIVIRANTAb and R. KETOLAb

aFinnish Environment Institute, Impacts Research Division, P.O. Box 140, FIN-00251Helsinki, Finland; bTechnical Research Centre of Finland, Chemical Technology, P.O.

Box 1401, F1N-02044 VTT, Finland

Aerial transport of organochlorines to Scandinavia as well as to Arctic areas has been observedin recent years. Atmospheric transport, wet and dry deposition and the tendency towards coldcondensation are likely the major reasons for many organochlorine compounds being detected innonpolluted northern areas. This paper presents the monthly collected bulk deposition results ofPAHs (31 congeners), PCBs (6 congeners) and HCHs (3 congeners) from the summer seasonsof 1993-1996. The detection limits for PAHs, PCBs and HCHs vary from 0.01 to 1 ng/1 anddepositions were calculated as micrograms per square metre. The deposition of PAHs have beenclearly decreasing both in Lapland and in southern Finland. The deposition of PCBs have beenabout three times larger in 1994 and 1995 than in 1993 or 1996 in Lapland. PCB deposition in1995 was also two to three times larger than in other years in southern Finland. There have notbeen any trends in the deposition of HCHs in Lapland, but in Southern Finland HCH depositionhas clearly been smaller from 1994-1995 than in other years.

Keywords: Atmospheric transport; bulk deposition; Finland; PAHs; PCBs; HCHs

INTRODUCTION

Significant concentrations of persistent harmful organic compounds in sedi-ment, fish, birds and marine mammals in Scandinavia have been observedsince the 1970s. Measurable levels of these organochlorines have been foundin areas situated not only near the local emission areas but also in headwaterlakes far away from local point sources.11'21

Evidence of aerial transport of organochlorines to Scandinavia and to theArctic has been observed in recent years. Atmospheric transport and wet and

* Corresponding author

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38 M. KORHONEN et al.

dry deposition is likely to be one of the major sources of many organochlorinecompounds to nonpolluted areas in the northern hemisphere, where numerousvolatile compounds have a tendency towards cold condensation.11'21

In the summers of 1993-1996, bulk depositions were collected in centralFinland (Evo), northern Finland (Oulanka 1993-1994) and Pallas (1995-1996)during five or four months, respectively. Organochlorines like PCBs, PCBzs,chlorophenols, pesticides and PAHs were analysed from the bulk deposition.In this study there are PAHs (31 congeners), PCBs (6 congeners) and HCHs(3 congeners) under discussion.

In Finland mainly industrially produced PAH is used in wood preservingmaterials like creosote oil. It contains for example antracene and benzo-(a)pyrene. Creosote oil produced in Poland and Germany contains 2-5%PAH compounds with 3 to 6 aromatic rings. The concentration of very toxicbenzo(a)pyrene is 0.03-0.12%. Creosote oil contains naphthalenes and alky-lonaphthalenes 15-25%, and its use in Finland is between 10,000-30,000tonnes.

Since 1989 it has been prohibited to produce or import PCBs to Finland.From the beginning of 1995 PCB, containing transformers and condensershave to be removed from use. The concentration level that is set for PCBcontaining products is >50 mg PCB/kg. The approximate annual usage ofPCBs in Finland has been 2000 tonnes.

The use and import of so-called 'classic' pesticides like DDT, lindane, HCBhas been forbidden in Finland since the 70 s. They are allowed to be importedand used only for research purposes. The last permit granted to use thesepesticides was for lindane to make pills from the seeds of turnip rape. Thisproduct is called Gamatin. Its production and usage has been forbidden fromJune 30, 1988.

MATERIAL AND METHODS

Precipitation studies in Finland have been done in the summertime both incentral Finland and in Lapland. The research sites have been in the Evo region(all four years) located in the southern part of Central Finland; in the Oulankaregion (1993-1994) in the south-eastern part of Lapland, and in the Pallasregion (1995-1996) located in western Lapland. (Figure 1)

The precipitation sampling was done with two glass funnels (30 cm indiameter). The funnels were set up 1.5-2.0 metres above the ground. Rain-water was collected through the funnels into 5-litre Pyrex bottles (buried inthe ground) using a teflon tube (14 mm). Before the start of the each sampling

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BULK DEPOSITION OF PAHs 39

FIGURE 1 The bulk deposition monitoring sites in Finland: Evo (1993-1996), Oulanka (1993-1994) and Pallas (1995-1996).

period the bottles, funnels and tubes were washed with ethyl alcohol, deion-ized water (purity class = I = conductivity < 0.005 mS/m). Then 100 mldichloro-methane (Merck n:o 6054) and 100 ml deionized water was addedto the bottles. The sampling period was about 3-5 weeks. The method usedwas a bulk sampler modified by DMU, The National Environmental ResearchInstitute, Denmark. The intercomparison of sampling methods for depositionmeasurements of organic compounds has been done in a joint project underthe Nordic Council of Ministers.'31

Determination Equipment

A gas Chromatograph, Hewlett Packard 5890 Series II (Hewlett Packard Co,Palo Alto, CA, USA), equipped with two electron capture detectors (ECD)and two capillary columns with different polarity (SPB-35, 30 m, 0.25 mm,0.25 urn, SP-5, 30 m, 0.25 mm, 0.25 urn, Supelco, Inc., Bellefonte PA, USA).Analyses were carried out using a splitless injection and temperature pro-gramme: from 50°C (1.5 min) to 150°C and to 260°C (15 min). The temper-ature of the injector was 260 °C and that of the detectors 300 °C.

A gas Chromatograph, Hewlett Packard 5790, (Hewlett Packard Co, PaloAlto, CA, USA), equipped with a mass selective detector, Hewlett Packard

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40 M. KORHONEN et al.

5970, and a capillary column (DB-17, 30 m, 0.25 mm, 0.15 urn, J & W Scien-tific, Folsom CA, USA). Analyses of PAH compounds were carried out usinga split injection and temperature programme: from 60°C to 160°C and to300 °C (17 min). Analyses of chlorinated pesticides were carried out using asplitless injection and temperature programme: from 80 °C (3.5 min) to 295 °C(20 min). The temperature of the injector was 280 °C and that of the transferline 280 °C.

Determination of PAH Compounds and Chlorinated Pesticides

The total volume of the samples was measured before extraction. The internalstandards (pyrene-dio, ß,ß-binaphthyl, indeno(l,2,3-cd)fluoranthene and ald-rine) were spiked to the samples before extraction. The samples were extractedonce with dichloromethane and three times with hexane. If needed, the analyteswere salted out with sodium chloride (NaCl). The extracts were combined,dried with sodium sulphate (Na2SO4), concentrated with a rotavapor to avolume of five mL and finally with a stream of pure nitrogen to a volume of0.5 mL. If needed, the final samples were purified by solid phase extraction.The samples were analysed by gas chromatography-mass spectrometry (GC-MSD) using the internal standard method and SIM-technique. The limit ofdetermination for PAH compounds was 0.1 ng/L and for chlorinated pesticides0.01 ng/L. Measurement uncertainty of the analyses is ±30%.

Determination of Polychlorinated Biphenyls (PCB)

The total volume of the samples was measured before extraction and about halfof the sample was taken for analysis. The internal standard (2,4,6 tribromo-biphenyl) was spiked to the samples before extraction. The samples wereextracted with hexane and acidic diethylether. The combined extracts wereacetylated with acetic anhydride and purified and fractioned by solid phaseextraction. The samples were analysed by gas chromatography (GC-ECD)using the internal standard method. The limit of determination for PCB com-pounds was 1 ng/L. Measurement uncertainty of the analyses is ±30%.

RESULTS AND DISCUSSION

The bulk depositions of PAHs, PCBs and HCHs were calculated as microgramsper square metre. The magnitude of the precipitation was calculated from thedata of the Finnish Meteorological Institute. The locations of the precipitationstations were: Lammi Iso-Evo in Evo; Kuusamo Kiutaköngäs in Oulanka; and

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BULK DEPOSITION OF PAHs 41

Muonio kk Alamuonio in Pallas. The uncertainty of the analyses has beentaken into account in the discussion concerning the deposition levels.

The deposition of PAHs has decreased significantly in Evo from 1993 toa quite stabilized level over the following three years (Figure 2). In Lapland

S

PA

H(J

200-

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50-

I.6 7

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II8 9

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1 - n8 9 10 m

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nd 1 nd _ • _ • n6 7 8 9 10 m

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6 7 8 9 10 m

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(a)

(b)

FIGURE 2 The bulk deposition of PAHs in Finland in years 1993-1996 (10~6 g/m2). Tothe sum of PAHs are calculated together 31 PAH congeners (naphthalene, 2-methylnaphtha-lene, 1-methylnaphthalene, bifenyl, 3-methylbiphenyl, acenaphthene, dibenzofurane, fluorene,dibenzotiophene, phenanthrene, anthracene, 2-methylanthracene, 1-methylanthracene, fluoran-thene, pyrene, benzo(a)fluorene, benzo(b)fluorene, benzo(b)nafto(2,l-d)tiophene, benzo(b)nafto-(l,2-d)tiophene, benz(a)anthracene, chrysene/triphenylene, benzo(b)-fluoranthene, benzo(k)fluo-ranthene, benz(e)pyrene, benz(a)pyrene, peryene, indeno(l,2,3-cdjpyrene, dibenz(ah)anthracene,benzo(ghi)peryene and coronene).

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42 M. KORHONEN et al

the decrease of PAHs was quite similar to that of southern Finland but notas quick or as strong. The high deposition of PAHs in 1993 could be fromincomplete burning processes in forest, peat or dumping areas. The decreasedPAH deposition levels after 1993 could be the result of improved processesin blast furnaces in the heavy metal industry or in power and heating plantprocesses.

A very high deposition of PAHs was observed in 1993 in Evo at the begin-ning of August and in October. The main congeners were, in both months,phenanthrene, fluoranthene and pyrene, and in October antracene as well.The highest deposition of PAHs in 1993 in Oulanka was observed in June,August and September. The main congeners in Lapland have also been phenan-threne, fluoranthene and pyrene. The same main congeners dominated thesum of PAHs in Lapland and in southern Finland from 1994-1996. The samemain congeners in deposition have also been detected in Rörvik, in southernSweden. The estimated total annual deposition of PAHs (about 0.1 mg/m2 yearin southern Finland in 1993) were the same as in southern Sweden.'41

The deposition of PCB s was about two to three times higher in year 1995than in other years in southern Finland (Figure 3). In Lapland, the PCB depo-sition in 1995 was also three times higher than in 1993 or 1996. In 1994 inLapland PCB depositions were high early in the summer. The highest depo-sition of PCBs have usually been in early summer both in Lapland and insouthern Finland. High levels were also found in Pallas in October 1995.The main PCB congeners were the IUPAC-numbers 153 and 138 both inLapland and in southern Finland. Little less than these congeners were foundthe numbers 180 and 101.

The calculated estimate about the PCB emissions in Finland in year 1995 isless than one ton. The calculations are based mainly on energyproduction andtraffic. When compared the emissionestimates with the deposition levels, insouthern Finland in other years than 1995 and in Lapland in 1993 and 1996, thedeposition levels indicates about ten times larger emissions than calculated. InLapland expecially local emissions are much smaller than in southern Finlandand the long range transport of PCBs could be the major input rate of PCBs.In southern Finland in 1995 the deposition levels were much bigger than inother years. It is suspected that a local reason for the increased PCB depositioncould be a different kind of burning or other methods of destroying concerningthe prohibited PCB containing materials, particularly in year 1995.

The highest deposition of HCHs was found in Lapland in 1993 and 1994 inearly summer (Figure 4). The large magnitude of precipitation in Evo in Junein 1993 and 1996 were one reason for the very high level of HCHs per squaremetre. The deposition of HCHs in southern Finland was in 1993 and 1996

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BULK DEPOSITION OF PAHs 43

(a)

6 7 8 9 10 m

1993

8 9 10 m

1996

(b)

FIGURE 3 The bulk deposition of PCBs in Finland in years 1993-1996 (1(T6 g/m2). Totalamount of PCB compounds = 2, 7 x sum c¡, where c; is the amount of a single PCB congener(IUPAC numbers 52, 101, 118, 138, 153, 180).

about three to four times higher than from 1994-1995. The biggest depositionwere found early in the summer season. The main congenere has been bothin Lapland and in southern Finland gamma-HCH. Also alfa-HCH has foundand much less than these beta-HCH.

The annual deposition of HCHs per square metre in Finland is about thesame level as in Sweden.141 In Denmark the HCH deposition is estimated to

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44 M. KORHONEN et al.

si 1-1

• ! • • - ñ7 S 9 10 m 6 7 8 9 10 m

• . ¡ • • I n6 7 8 9 10 m 6 7 8 9 10 m

(a)

i..6 7 8 9 10 IT

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EVO

I . l i n i - I I6 7 8 9 10 m

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6 7 8 9 10 m

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un6 7 8 9 10 m

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(b)

FIGURE 4 The bulk deposition of HCHs in Finland in years 1993-1996 (1(T6 g/m2). To thesum of HCHs are calculated three congeners (alpha-, beta- and gamma-HCH).

be twice as big as in Finland; in Norway three times and in Germany fivetimes the deposition of Finland's. The use of lindane was banned in 1988in Finland, in 1989 in Sweden and in 1991 in Norway.[4-5-6'7'8] Because ofthe global distribution of HCHs, the differences in the deposition could be anindication of the usage of HCHs in the warmer areas in the world, where theyare still used as pesticides.'^

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BULK DEPOSITION OF PAHs 45

References

[1] The Science of the Total Environment. (1995). Special Issue: Ecological Effects of ArcticAirborne Contaminants. Elsevier, 160/161.

[2] EMEP. Proceedings of the first workshop on emissions and modelling of atmospheric trans-port of POPs and heavy metals. EMEP/CCC-Report:7/93, (1993).

[3] A. Kiviranta, et al. (1993). Intercomparison of sampling methods for deposition measure-ments of persistent organic compounds. Finnish Chem. Congr. Kemia.

[4] E. Brorström-Lunden (1995). Measurements of Semivolatile Organic Compounds in Air andDeposition. Dep. of Anal. and Marine Chem. Univ. of Göteborg.

[5] M. Cleemann, M. E. Poulsen and G. Hilbert (1995). Deposition of lindane in Denmark.Chemosphere, 30(1), 2039-2049.

[6] W. Jaeschke, B. Gath and D. Pfäfflin (1995). Deposition monitoring of pesticides in southernGermany. TemaNord, 558, ISBN 92 91206784.

[7] O. Lode, O. M. Eklo, H. Börge, A. Svesen and Å. M. Johnsen (1995). Pesticides in precip-itation in Norway. TemaNord, 558, ISBN 92 91206784.

[8] J. Siebers, D. Gottshield and H. G. Nolting (1995). Deposition of pesticides in northernGermany. TemaNord, 558, ISBN 92 91206784.

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