Polychlorinated Naphthalenes inSediment and Biota from theGdansk Basin, Baltic SeaJ E R Z Y F A L A N D Y S Z * A N DL I D I A S T R A N D B E R G

Department of Environmental Chemistry &Ecotoxicology, University of Gdansk,ul. Sobieskiego 18, PL 80-952 Gdansk, Poland

P E R - A N D E R S B E R G Q V I S T ,S T E N E R I K K U L P ,B O S T R A N D B E R G , A N DC H R I S T O F F E R R A P P E

Institute of Environmental Chemistry, University of Umea,S-901 87 Umea, Sweden

To identify potential sources and accumulationfeatures concentrations, profiles, and patterns of poly-chlorinated naphthalene (PCN) residues weredetermined in sediment, mussel, crab, plankton, andfishes from the Gdansk Basin, Baltic Sea. Differentmarine organisms of the lower food web clearly bio-accumulate many PCN congeners. Depending onthe matrix type, PCNs substituted with four or five chlo-rines dominate. Due to the characteristic profileand pattern of PCN congener groups found in subsurfaceplankton, mussel, and surface sediments, depositionfrom the atmosphere is postulated to be the mainsource of these pollutants. Nineteen of 22 tetra-, all14 penta-, 9 of 10 hexa-, and both hepta-CNs couldbe quantified in the samples. The patterns of tetra-,penta-, and hexa-CNs varied largely between thesamples or groups of the samples as well as whencompared to the technical PCNs formulation Ha-lowax 1014. This implies different absorption/retentionrates and/or marked, structure-dependent metabolismof some PCN congeners by marine species.

IntroductionPolychlorinated naphthalenes (PCNs) represent a group of75 compounds that are relatively well soluble in lipids andorganic solvents and have physical and chemical propertiessuch as melting point, volatility, water solubility, octanol-water partition coefficients (KOW), bioconcentration factors(BCF), adsorption coefficients in sediments (KOC), andHenry’s law constant (H), which favor their environmentalpersistency and bioaccumulation (1-7). These chemicalsare ubiquitous pollutants; hovewer, knowledge on envi-ronmental fate, distribution, and accumulation in the biotaof many PCN congeners found in the technical formulationsis very limited (4).

Polychlorinated naphthalenes are primairly industrialchemicals (1, 8) and were introduced into a commonpractice at the beginning of this century; however, theirsources in the environment are related also to the byprod-ucts of human activities due to combustion and chlorinationprocesses (9-24). Halowax is a trade name of a technicalPCN product manufactured in the United States, and atleast France, Germany, Italy, and Great Britain also hadtheir own PCN formulations (25-27). The synthesis of PCNson a technical scale was voluntary ceased in United Statesin 1977, while some volumes were produced in westernEurope until the mid 1980s (4). Learning from the lessonwith polychlorinated biphenyls (PCBs), it seems possiblethat PCNs potentially were synthesized in technical scalealso in some other countries (for example, it was untilrecently rather unknown that Poland had its two owntechnical PCB formulationssChlorofen, which is similarin appearance and composition to Aroclor 1262 (28), andTarnol, which is similar to Aroclor 1254). There are onlyrough estimates of the world (United States and westernEurope) production volume of PCNs. This volume isassessed to be around 10% of the total production of PCBs(29), which is around 1 500 000 t for the United States,western Europe, Japan and Australia, including also theformer USRR and Czechoslovakia (30, 31), while virtuallynothing is known on the type and quantity of PCNspotentially manufactured in other coutries.

1-Chloronaphthalene is a liquid at room temperature(1, 8) and is used as an organic solvent and additive inindustrial chemical processes. 1-Chloronaphthalene wasutilized in Xylamitssa popular wood (and other purpose)preservative widely applied in the past in Poland and alsocontaining technical pentachlorophenol together with thewaste products of chlorophenols distillation and othersubstances (32).

Technical PCN formulations are manufactured by thechlorination of molten naphthalene in the presence of iron-(III) or antimony(V) chloride (1, 8). Both electrophilic andnucleophilic substitution as well as radical attacks occurpredominantly in the R- (peri-; 1, 4, 5, and 8) positions onthe naphthalene skeleton (33, 34).

Nakano et al. (18) and Wiedmann and Ballschmiter (20)listed all 75 PCN congeners. The predominant PCNcongeners found in the equivalent mixture of Halowax 1000,1001, 1013, 1014, 1031, 1051, and 1099 (Equi-Halowax) aresuch individuals as PCNs 1, 5/7, 23/24, 33/34/37, 38/40,52/60, 61, 57, 62, 53, 59, 71/72, 69, and 74 (22). Among thetetra-, penta-, and hexa-CNs in Halowax 1014, PCNs 38, 33,46, 59, 62, 58, 57, 61, and 65 (18-20, 23) predominate. SuchPCN congeners as 39, 54, 55, and 70 were not found inHalowax 1014 (23). On the other hand, as much as 74 of75 possible PCN congeners are formed in various propor-tions throughout the radical reactions in the flame (22, 23),a process dependent on kinetic, thermodynamic, and stericeffects (17). In products such as fly ash and flue gas, formedin municipal solid waste incinerators (MSWI), PCNs 39, 54,60, 51, 52, and 66/67 (22, 23) predominate.

During tap water chlorination, mono- and di-CNs areformed (11), and nothing is known on the possibility offormation of higher chlorinated PCN congeners.

* Author to whom correspondence should be addressed; Fax: +48-58-410357; telephone: +48-58-415271, ext 272.

Environ. Sci. Technol. 1996, 30, 3266-3274

3266 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 30, NO. 11, 1996 S0013-936X(96)00057-0 CCC: $12.00 1996 American Chemical Society

+ +

+ +

Polychlorinated naphthalenes were identified in the pastin various biological samples, as reviewed by some authors(4); however, the analytical methods used were not specificenough to enable quantification of individual congeners.In more recent papers (21, 35) many PCN congeners werequantified in the environmental and technical samples;however, their structure was not shown. Some accuratelydefined PCN isomers were quantified recently in humanadipose tissue in Canada (36), in cod liver and guillemotegg from the Baltic Sea (37), in cod liver from the coastalarea of southern Norway (38), in a rice oil causing Yushopoisoning, in adipose tissue of Yusho victim, and intechnical PCB formulation of Kanechlor 400 (24).

Studies on environmental sources, concentrations,distribution, fate, and effects of PCNs using congener-specific and highly sensitive analytical methods, which aregenerally lacking, are required since these xenobiotics arewide spread in nature and many of them pose a high toxicpotential (39, 40).

Recently, nearly all theoretically possible isomers oftetra-, penta-, hexa-, and hepta-CN could be identified andquantified in tissues of white-tailed sea eaglessa top birdof prey in northern Europe (6)sin harbor porpoise fromthe Baltic Sea, and in black cormorants breeding at thecoast of the Gulf of Gdansk, Baltic Sea (7, 41).

Materials and MethodsCollection of Samples. Surface sediment, subsurfaceplankton, mollusk, crustacean, lamprey, and 10 species offishes were collected from the area of the Gdansk Basin in1992. The sampling locations are shown in Figure 1. Thecommon and latin names of organisms examined togetherwith the total number of the individuals and their lipidscontent and the results of chemical analysis are given inTable 1. A surface sediment sample (0-10 cm) was takenfrom the nearshore sedimentation area of the Wisla River(Vistula River) in Kiezmark under Gdansk in June 6, 1992.Sediments were air-dried, crushed, and Soxhlet-extractedwith toluene for 12 h. For the recovery measurements(internal standard) and extract cleanup, the procedure wasthe same as is given below for the biotic material. Asubsurface plankton sample (218 g wet wt) was taken in thecentral area of the Gdansk Deep during the research cruiseof R/V Oceania in September 1992. That sample consistedof several species of phyto- and zooplankton, and thedominating genera were such as Chaetoceros, Coscinodiscus,

Nodularia, Anabaena, Prosocentrum, Aphanisomenon, Co-papoditi, Nauplii, Bosnina, Keratella, and Cladocera. Mus-sels (350 specimens, ca. 1.5-4 cm long) were taken by grabsampler, while crab and fishes, except for stickleback, werenetted using a bottom trap situated several meters out fromthe harbor of the port of Gdynia. Adult sticklebacks ofboth sexes were collected using a hand net directly fromthe harbor in Oksywie (ca. 2 km north of the site where allother fishes were collected). In the case of lamprey, herring,eelpout, and round goby, adult specimens with body lengthbetween 16 and 26 cm were selected. For other specimens,the individuals were small in size, i.e., flounders, lesser sandeel, and sand eel were ca. 13 cm in body length; for perch,it was between 10 and 17 cm; for pikeperch, it was ca. 15cm; and for cod, it was ca. 20 cm. All animals were deepfrozen (-20 °C) directly after capture and kept in suchcondition in clean polyethylene bags until chemical analysis.Pooled samples, containing from 3 to 30 whole fishes orsoft tissue of 350 individual mussels, were subjected tochemical analysis.

Chemical Analyses. The analytical method used for thedetermination of chloronaphthalenes is a part of a multi-residue procedure performed in parallel analysis of manyorganochlorines and polynuclear aromatic hydrocarbons(PAH) (42). After homogenization of the sample (77-378g) with anhydrous sodium sulfate, which was baked at 550°C for 2 days, a powdered mixture was packed into a widebore open glass column, spiked with an internal standard([13C12]-3,3′,4,4′,5-pentachlorobiphenyl; PCB 126), extractedwith a 500 mL mixture of acetone and n-hexane (2.5:1) and500 mL of n-hexane and diethyl ether (9:1) to obtain a fatextract. Bulk lipid removal was performed by means of thepolyethylene film dialysis method (43, 44). After dissolvingthe extracted lipids in cyclopentane, dialysis through thepolymeric mebrane was accomplished by changing thedialyzate after 24, 48, and 72 h. The three dialyzate fractions,containing normally between 1 and 10% of the originallipids, depending on sample size and matrix type, werecombined and concentrated to a few milliliters using a rotaryevaporator. The extract was split into two parts, of which90% was used for analysis of PCNs and some other planarcompounds not described here, while 10% was used forthe analysis of organochlorine pesticides and the bulk ofPCBs. The remaining fat was removed on a combined silicacolumn packed as follows from the bottom: glass wool,potasium silicate (10 mL), a layer of neutral silica gel, 40%sulfuric acid silica gel (20 mL), and at the top a layer ofanhydrous sodium sulfate. The column length was 20 cm,and the diameter was 38 mm. The gravimetric elution ofplanar organochlorines was done with 200 mL of n-hexane,and 40 µL of tetradecane was added as a keeper beforeevaporation of the solvent. The extract was then fraction-ated on HPLC using an activated carbon column (AmocoPX-2; 2-10 µm, dispersed on LiChrospher RP-18; 15-25µm) (44, 45). Between the carbon column and the pre-column, a filter valve (Valco Instruments Co. Inc., TX) wasmounted, enabling backflush of the column. The elutionfrom the HPLC carbon column was performed with 1%methylene chloride in n-hexane for 7.5 min, solvent 1, andthen gradient elution up to 10% toluene, solvent 2, for 32.5min. Fraction one, containing organochlorine pesticidesand 2-4 ortho PCBs, is collected during the first 15 min,and fraction two, containing mono-ortho PCBs, is collectedbetween 15 and 40 min. The total volume of the solventsused was 160 mL, and the flow rate was 4 mL/min. PCNs

FIGURE 1. Sampling locations of plankton (P), sediment (S), andorganisms (F) in the Gdansk Basin.

VOL. 30, NO. 11, 1996 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3267

+ +

+ +

TA

BLE

1

Conc

entra

tions

ofPo

lych

lorin

ated

Naph

thal

enes

inSu

rface

Sedi

men

t(n

g/g

Dry

Wt),

Plan

kton

,Mus

sel,

Crab

,Lam

prey

,and

Fish

es(n

g/g

Lipi

dW

t)fro

mth

eGd

ansk

Basi

n,Ba

ltic

Seaa

PCN

no.

stru

ctur

e

sedi

men

tsu

rfac

e(0

-10

cm)

NA

b

plan

kton

mix

edsp

ecie

sca

.220

g1.

83

mus

sel

Myt

ilus

tross

ulus

350

1.30

crab

Carc

inus

mea

ns3 1.27

lam

prey

Lam

petra

fluvi

atili

s3 6.27

floun

der

Plat

ycht

his

flesu

s5 4.78

stic

kleb

ack

Gast

eros

teus

acul

eatu

s30 2.44

less

ersa

ndee

lAm

odyt

esto

bias

us20 5.48

sand

eel

Hepe

ropl

usla

nceo

latu

s20 5.73

Bal

tiche

rrin

gCl

upea

hare

ngus

3 9.00

perc

hPe

rca

fluvi

atili

s8 5.96

pike

perc

hSt

izos

tedi

onlu

ciop

erca

3 4.44

elep

out

Zoar

ces

vivi

paru

s3 3.02

roun

dgo

byN

eogo

bius

mel

anos

tom

us6 4.78

cod

Gadu

sm

orhu

a3 3.40

Tetr

achl

oron

apht

hale

nes

421,

3,5,

7-T

4CN

0.18

0.46

5.1

420.

643.

211

3.2

2.2

3.5

1.3

171.

628

1.9

33/3

4/37

1,2,

4,6-

/1,2

,4,7

-/1,

2,5,

7-T

4CN

1.5

1.5

1742

0.52

1.0

174.

02.

22.

60.

997.

00.

7518

0.47

471,

4,6,

7-T

4CN

0.67

0.69

7.0

3.7

0.55

0.29

5.6

2.0

1.2

1.9

0.58

4.1

0.28

140.

2736

/45

1,2,

5,6-

/1,3

,6,8

-T4C

N0.

097

0.07

90.

961.

60.

020

0.02

20.

510.

083

0.03

40.

096

0.02

70.

170.

031

0.35

0.01

928

/43

1,2,

3,5-

/1,3

,5,8

-T4C

N0.

096

0.78

119.

20.

038

0.37

7.1

2.1

1.3

1.3

0.65

3.2

0.58

150.

327

/30/

391,

2,3,

4-/1

,2,3

,7-/

1,2,

6,7-

T4C

N0.

027

0.18

2.6

1.4

0.05

0.04

11.

10.

250.

120.

240.

100.

360.

098

0.80

0.04

2

32/4

81,

2,4,

5-/2

,3,6

,7-T

4CN

0.01

40.

074

1.1

0.52

0.04

40.

071

1.3

0.16

0.08

00.

210.

120.

270.

091

1.2

0.04

535

1,2,

4,8-

T4C

N0.

084

0.42

7.5

8.1

0.43

0.64

7.3

1.6

0.91

1.8

0.92

3.3

0.69

130.

2638

/40

1,2,

5,8-

/1,2

,6,8

-T4C

N2.

01.

216

5.7

0.31

0.27

5.2

1.5

0.64

0.84

0.51

2.6

0.57

4.5

0.33

461,

4,5,

8-T

4CN

0.74

0.53

7.4

7.4

0.16

0.19

3.6

0.59

0.01

50.

610.

391.

70.

502.

70.

1941

1,2,

7,8-

T4C

N0.

120.

079

1.1

1.2

0.01

50.

018

0.32

0.02

90.

0039

0.03

20.

016

0.15

0.04

50.

140.

020

tota

ltet

ra-C

Ns

5.5

6.0

7712

02.

86.

160

168.

713

5.6

405.

298

39

Pent

achl

oron

apht

hale

nes

52/6

01,

2,3,

5,7-

/1,2

,4,6

,7-

P5C

N0.

140.

297.

469

1.6

7.4

193.

72.

34.

55.

719

8.4

453.

7

581,

2,4,

5,7-

P5C

N0.

450.

037

1.0

8.2

0.04

21.

61.

60.

260.

270.

490.

442.

20.

615.

30.

3561

1,2,

4,6,

8-P

5CN

0.08

50.

346.

954

0.38

6.6

112.

11.

74.

43.

317

2.8

472.

650

1,2,

3,4,

6-P

5CN

0.02

90.

082

2.2

110.

042

0.36

1.6

0.50

0.34

0.26

0.07

00.

480.

089

4.1

0.02

851

1,2,

3,5,

6-P

5CN

0.03

10.

030

0.86

3.6

0.02

10.

150.

870.

140.

140.

064

0.03

90.

170.

042

0.93

0.01

854

1,2,

3,6,

7-P

5CN

0.00

740.

014

0.21

0.33

0.00

540.

0048

0.34

0.06

40.

063

0.15

0.05

60.

092

0.05

80.

460.

014

571,

2,4,

5,6-

P5C

N0.

056

0.12

2.3

7.3

0.12

1.8

5.6

0.74

0.74

1.0

0.41

2.4

0.30

110.

2962

1,2,

4,7,

8-P

5CN

0.07

00.

155.

410

0.13

1.2

5.7

1.2

1.1

1.3

0.59

1.8

0.56

190.

3153

/55

1,2,

3,5,

8-/1

,2,3

,6,8

-P

5CN

0.08

20.

153.

02.

20.

140.

742.

60.

790.

751.

00.

381.

80.

3713

0.18

591,

2,4,

5,8-

P5C

N0.

070

0.16

4.4

8.9

0.13

1.2

4.2

0.70

0.57

1.3

0.85

1.9

0.73

9.7

0.26

491,

2,3,

4,5-

P5C

N0.

074

0.01

40.

610.

330.

014

0.07

60.

410.

063

0.05

10.

100.

048

0.14

0.05

31.

30.

016

561,

2,3,

7,8-

P5C

NN

D0.

0056

0.14

0.42

0.03

10.

0086

0.12

0.02

80.

020

0.04

20.

032

0.02

60.

015

0.12

0.00

61to

talp

enta

-CN

s1.

11.

434

180

2.6

2153

108.

015

1247

1416

078

Hex

achl

oron

apht

hale

nes

66/6

71,

2,3,

4,6,

7-/

1,2,

3,5,

6,7-

H6C

N0.

033

0.07

20.

305.

70.

401.

20.

590.

097

0.13

0.45

0.52

0.37

1.3

2.4

0.35

64/6

81,

2,3,

4,5,

7-/

1,2,

3,5,

6,8-

H6C

N0.

012

0.01

60.

192.

90.

023

0.96

0.30

0.03

90.

052

0.21

0.14

0.23

0.17

0.65

0.17

691,

2,3,

5,7,

8-H

6CN

0.01

80.

019

0.21

8.3

0.41

4.2

0.47

0.05

70.

063

0.39

0.45

0.22

0.61

2.0

0.50

71/7

21,

2,4,

5,6,

8-/

1,2,

4,5,

7,8-

H6C

N0.

0082

0.01

90.

263.

00.

066

1.4

0.29

0.04

20.

034

0.34

0.68

0.93

0.79

0.06

40.

29

631,

2,3,

4,5,

6-H

6CN

0.00

660.

0093

0.26

0.84

0.00

760.

420.

140.

017

0.01

80.

064

0.02

90.

150.

038

0.53

0.03

665

1,2,

3,4,

5,8-

H6C

N0.

0033

0.00

70.

160.

260.

013

0.41

0.09

60.

023

0.02

20.

054

0.08

50.

060

0.09

80.

082

0.03

4to

talh

exa-

CN

s0.

081

0.14

1.4

210.

928.

61.

90.

280.

321.

51.

92.

03.

05.

71.

4

Hep

tach

loro

naph

thal

enes

731,

2,3,

4,5,

6,7-

H7C

N0.

012

0.01

60.

055

0.42

0.01

70.

210.

030

0.00

450.

003

0.08

0.00

5N

D0.

0050

0.07

0.00

474

1,2,

3,4,

5,6,

8-H

7CN

0.01

20.

016

0.05

50.

410.

009

0.10

0.01

70.

0015

0.00

10.

070.

0047

ND

0.00

250.

050.

001

tota

lhep

ta-C

Ns

0.02

40.

032

0.11

0.83

0.02

60.

310.

047

0.00

60.

004

0.15

0.00

97N

D0.

0075

0.12

0.00

5to

talP

CN

s6.

77.

611

032

06.

336

120

2617

2919

8922

260

13a

Co

lum

nh

ead

ing

sre

pre

sen

tsa

mp

lety

pe,

Lati

nn

ame,

volu

me

(g)

or

nu

mb

ero

fsp

ecie

s,an

dlip

ids

con

ten

t(%

).b

NA

,n

ot

app

licab

le.

cN

D,

no

td

etec

ted

.

3268 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 30, NO. 11, 1996

+ +

+ +

together with PCDDs, PCDFs, and non-ortho planar PCBswere reverse eluted in fraction three with 80 mL of toluene(Burdick and Jackson, Muskegon, MI), degassed with argon.The eluate was concentrated and spiked with [13C12]-2,2′,4,5,5′-pentachlorobiphenyl (PCB 101) as the recoverystandard and evaporated to a final volume of 30 µL withtetradecane added as a keeper.

A gas chromatograph (Hewlett Packard 5890 GC) coupledto a mass spectrometer (VG Analytical 11-250 J, Altrincham,United Kingdom) was used for the determination of PCNcongeners. Injections were made using splitless mode, andthe oven was temperature programmed as follows: initialtemperature 180 °C; initial time 2 min; rate 1, 20 °C/minto 200 °C, rate 2, 4 °C/min to final temperature 300 °C andfinal time 15 min. A Rtx-5 fused silica capillary column (60m × 0.32 mm i.d.), coated with crossbond 5% diphenyl-95% dimethyl polysiloxane with a film thickness of 0.25 µmwas employed for the analysis. The ion source was keptat 250 °C and operated under electron ionization (EI)conditions at 70eV, and the MS was tuned in the selectedion monitorng (SIM) mode. For the confirmation/quantification of PCNs, the two most abundant ions in thechlorine cluster of the molecular ion were monitored atm/z 263.9 and 265.9 for tetra-CNs, m/z 297.9 and 299.9 forpenta-CNs, m/z 331.8 and 333.8 for hexa-CNs, and m/z365.8 and 367.8 for hepta-CNs. Isotopically labeled PCBs126 (internal standard) and 101 (recovery standard) wereused for compensation of possible losses during theenrichment procedure. A procedural blank was performedwith every set of the real samples analyzed. The technicalmixture Halowax 1014 was used to determine elution orderand pattern of PCNs in the sample chromatograms.Appropriate chromatographic data published for Halowax1014 by Wiedmann and Ballschmiter (20), Nakano et al.(18), Takasuga et al. (22), and Imagawa and Yamashita (23)were used to identify the ellution pattern of tetra- to hexa-CNs on the Rtx-5 capillary column chromatograms in thisstudy. In one of the papers (18), the congeners ofchloronaphthalene have been characterized but the struc-tures have not in all cases been unquestionably determined.PCNs 66/67, 71, and 73 (synthesized by Dr. Eva Jakobsson,Stockholm University) were native standards used togetherwith the above-mentioned PCBs 101 and 126 for GC/MSquantification based on the peak area, and the results werecorrected for recoveries. The hexa- and hepta-CNs werequantified on the basis of the molar response (MR) factorsof congeners 66/67, 71, and 73, respectively. Since thestandards of individual native mono- through penta-CNsor their 13C12-labeled analogues were not available duringthe course of analysis, the MR (SIM) factors of hexa-CNswere used to quantify the tetra- and penta-CNs withoutcorrection for the differences in the ionization cross-section(Q), which is 33.7, 36.9, and 40.1× 10-16 cm2 for the tetra-,penta-, and hexa-CNs, respectively (20).

Results and DiscussionPolychlorinated naphthalenes were detected in the WislaRiver surface sediment and in all biological samples (Table1). Such species as crab, round goby, mussel, and stick-leback showed highest concentrations of the total PCNsbetween 110 and 320 ng/g, and for other biological samplesit was from 6.3 to 89 ng/g lipid weight. The lipid-weightbased concentrations of the total PCNs in whole fishes wereindependent of the lipid contents of fish. Apart from theconcentration of the total PCNs, there are also substantial

differences in the profile of congener groups as well as inthe patterns of tetra-, penta-, and hexa-CNs between varioussamples analyzed; however, some similarities also couldbe observed (Figures 2-4 ).

PCNs were quantified recently also in the muscle tissueand/or liver of pike, burbot, cod, and herring from theSwedish waters (35) and in liver of cod from Norway (38).Since only a few PCN congeners were found/measured orreported in fishes in both the above-cited contributions(35, 38), the data gained cannot be compared with the totalPCN concentrations quantified in this study and presentedin Table 1. Nevertheless, some of the isomers of penta-CN(35) were found in pike from the Swedish lakes (especiallyLake Jarnsjon) in much higher concentration than in fishesfrom the Gulf of Gdansk, and the reason is mainly becauseof a significant point pollution source in the area.

Congener Groups Profile. Halowax 1014 is the for-mulation containing naphthalene (0.3%), and all homologuegroups such as mono- (0.4%), di- (0.3%), tri- (2.8%), tetra-(18.2%), penta- (46.8%), hexa- (23.0%), hepta- (1.6%), andocta-CN (6.6%) (20). The vacuum-distilled Nibren D130 aswell as dark colored non-vacuum-distilled Nibren RN 130waxes are the German PCN technical mixtures and aresimilar in chloronaphthalene homologue group composi-tion (%) to Halowax 1014 (46). Unfortunately, a detailedknowledge of PCN congener composition of these twoEuropean formulations is lacking. The profile of PCNcongener groups in Halowax 1014 is quite different fromthose found in the sediment sample and most of theorganisms examined. There is only a rough similaritybetween the congener group profile of tetra (16.9%), penta-(58.48%), hexa- (23.76%), and hepta-CNs (0.86%) in flounderand Halowax 1014.

In this study surface sediment, plankton (mixed phyto-and zoo-) and mussel in their profile of PCN congenergroups show very high contribution from tetra-CNs (be-tween 68.13 and 82.17%) (Table 1). The knowledge onvolatility of individual PCNs is very scare. Tetra-CNs havemuch higher vapor pressure (estimated value of 3.6× 10-4

mmHg for PCN 37) than penta- (3.2× 10-5 mmHg for PCN52), hexa- (7.1 × 10-6 mmHg for PCN 64), hepta- (2.8 ×10-6 mmHg for PCN 74), and octa-CN (1.0 × 10-6 mmHg;PCN 75) (4). The differences in voltality of different PCNhomologue groups can prefer the higher environmentalmobility of lower chlorinated congeners. A specific com-position (%) of PCN homologue groups in the sedimentsas well as in the biological matrices like plankton andmussel, with a higher proportion of tetra- and penta- thanhexa- and hepta-CNs, seems to support such a hypothesis.This finding can suggest the atmosphere as a main routeof transportation, deposition, and source of PCNs to theGdansk Basin.

Congener Pattern. Tetrachloronaphthalenes. Thereare 22 theoretically possible isomers of tetra-CN, of which19 can be present in the sediment and biota samples (Table1). Fourteen tetra-CN isomers were not well resolved onefrom the another during a run on the Rtx-5 60-m longcapilary column selected for gas chromatographic separa-tion and formed six peaks on the chromatogram. Thereare large differences in the pattern of tetra-CNs found insediments and biological samples when compared toHalowax 1014, and such differences are also observed forvarious organisms (Figure 2). Nevertheless, there are somesimilarities in pattern of tetra-CNs for different groups offishes and between mussels. Depending on the type of the

VOL. 30, NO. 11, 1996 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3269

+ +

+ +

FIGURE 2. Pattern of tetrachloronaphthalenes in biological samples, sediment, and Halowax 1014 [data for Halowax were taken fromImagawa et al. (19), and details of the isomers numbering are explained in Table 1].

3270 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 30, NO. 11, 1996

+ +

+ +

FIGURE 3. Pattern of pentachloronaphthalenes in biological samples, sediment, and Halowax 1014 [data for Halowax were taken fromImagawa et al. (19), and details of the isomers numbering are explained in Table 1].

VOL. 30, NO. 11, 1996 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3271

+ +

+ +

FIGURE 4. Pattern of hexachloronaphthalenes in biological samples, sediment, and Halowax 1014 [data for Halowax were calculated fromWiedman and Ballschmiter (20), and details of the isomers numbering are explained in Table 1].

3272 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 30, NO. 11, 1996

+ +

+ +

matrix investigated, PCNs 42, 33/34/37, 28/43, 35, and/or38/40 were the dominating isomers among tetra-CNs. PCN42 is only a minor (1.2%) constituent among tetra-CNs inthe technical Halowax 1014 (19, 23) and Equi-Halowaxmixtures, which contain all theoretically possible PCNcongener groups (18, 22). Contrary to its low abundancein Halowax formulations, PCN 42, which is a symetricalmolecule substituted in two reverse-opposite peri- andtwo reverse-opposite lateral positions, seems to be verypersistent in the environmental conditions and is the mostabundant component among tetra-CNs in most of the fishesexamined. PCNs 33/34/37 form a single peak on the Rtx-5chromatogram and occupy altogether 21.7% in Halowax1014 (19, 23) and 8.5% in Equi-Halowax (18, 22). Thesethree isomers dominate among tetra-CNs in plankton andmussels as well as in nearshore and mainly feeding onplankton fish species such as lesser sand eel, stickleback,and sand eel. PCNs 33/34/37 are very abundant also insediment, crab, and many other fishessapart from cod andflounder. PCN 28 (with 0.6%) and 43 (with 8.8%) contrib-uted 9.4% to tetra-CNs in Halowax 1014 (19, 23) and 11.4%to the total PCNs in Equi-Halowax (18, 22). Both theseisomers occupied from 7.80 to 15.36% (except of 1.38% inlamprey) in fishes, from 7.49 to 14.33% in crab, plankton,and mussel, and only 1.74% in sediment (Figure 2). PCNs38 and 40 also elute unresolved from the Rtx-5 column andform a single peak on a chromatogram. These twocompounds represent, respectively, 36.8 and <0.2% of tetra-CNs in Halowax 1014 (19, 23) and 34.1 and 0.2% of tetra-CNs in Equi-Halowax (18, 22). Nevertheless both theseisomers contribute highly to the total tetra-CNs especiallyin the sediment, plankton, and mussel samples.

When considering differences in the pattern of tetra-CNs between the particular samples, there is a largesimilarity between plankton and mussel, and only a weaksimilarity between these two biological matries and sedi-ment and/or Halowax 1014. The pattern of tetra-CNs incrab, with two highly dominating peaks from PCNs 42 and33/34/37 is quite different from that in any other biological,abiotic, or technical Halowax 1014 (Figure 2). A matrixsuch as surface sediment and to some degree also musseland plankton, both with potentially low possibilities todegrade persistent organochlorines, seem to well reflectthe composition of tetra-CNs potentially deposited fromthe air and also present in the water column. However, noquantitative and qualitative data exist to support thathypothesis. In the exhaust gas from the MSW incineratordi-/tri-CNs dominate, followed by tetra-, penta-, hexa-,hepta-, and octa-CN (47). There are large differences inabundance of the particular isomers of tetra-CN betweenthese three matrices alone and also when compared toHalowax 1014 (Figure 2). It is actually difficult to say thatdifferences are due to different deposition patterns ordifferences in absorption/metabolism rates of some tetra-CNs.

Some of the fish species in this study show very similarcomposition of tetra-CNs, while lamprey, with highlycontributing PCN 47, exhibits a totally different pattern(Figure 2). The pattern of tetra-CNs found in fishes andcrab differs from that in plankton, mussel, and sedimentand also of Halowax 1014, which indicates the possibilityof metabolism of various isomers of tetra-CN by those, whoare relatively higher in their position in the marine foodweb, animals.

Pentachloronaphthalenes. There are 14 theoreticallypossible isomers of penta-CN, and all are potentially presentin the biological samples examined. PCNs 54 and 55 areabsent in Halowax 1014 (23) and probably also in Equi-Halowax (18, 22). On the other hand, PCN 54 is an abundantconstituent in fly ash and flue gas from the municipal solidwaste incinerators (MSWI), and PCN 55 is a minorcomponent in these matrices (22, 23). PCN 54 elutes fromthe Rtx-5 (an analogue phase to DB-5 and Ultra-2) capilarycolumn as a single compound and forms a well-resolvedpeak (18, 22) on the capillary column gas chromatogram.On the basis of the composition and chromatographiccharacteristic of penta-CNs in Halowax 1014 and the Equi-Halowax mixture (18, 20, 22, 23), it was possible to identifythe presence of PCN 54 on the HRGC-MS/EI-SIR chro-matograms of all environmental samples in this study.However, that isomer of penta-CN is only a minor con-stituent with between 0.023 and 1.03% in total PCNs inbiota and sediment (Table 1). Since PCN 54 has all fourlateral positions substituted with chlorine, that moleculecan be one of the most toxic PCNs. So its environmentalpersistence as well as its availability for the biota from thesources other than technical PCN formulations is strikingand seems to be of high research priority.

Three early eluting isomers of penta-CN, namely, PCNs52/60 and 61 are the most contributing compounds (from41.55 to 81.06%) to the total penta-CNs in biologicalsamples, while the early eluting PCN 58 occupies 41.12%in sediment (Figure 3).

The pattern of penta-CNs found in biological samplesand sediment is quite different from that in Halowax 1014(based on ref 19) (Figure 3). Plankton and mussel, togetherwith plankton-feeding fishes such as sand eel, lesser sandeel, herring, and stickleback, show a slight similarity in theirpatterns of penta-CNs. Lamprey, eelpout, and perch onone side and cod, pikeperch, and flounder, including crabon the other side also show similarity in their patterns ofpenta-CNs. For the round goby, which is rather a bottom-feeding fish and a totally new specimen in the Baltic Sea,the pattern of penta-CNs is slightly similar to that foundin fishes feeding mostly on plankton (Figure 3).

Hexachloronaphthalenes. Nine isomers of hexa-CNcould be quantified in all the biota samples and in thesurface sediment of this study (Table 1, Figure 4). Thesenine isomers occur also in Halowax 1014 and Equi-Halowaxmixtures, while PCN 70 is absent (18, 20, 22, 23). PCNs66/67 remained unresolved one from the other on manyliquid phases of different polarity that were tested andusually employed in capillary gas chromatographic separa-tion of PCNs and PCBs (polychlorinated biphenyls) (36, 37,48). These two congeners were found in some studies tobe highly bioaccumulative in female Spraque-Dawley ratsorally dosed with Halowax 1014, while all other chlo-ronaphthalenes were readily metabolized (5, 39). In someearlier studies, PCNs 66/67 were the main hexa-CNs foundin fishes, white-tailed sea eagle, and grey seal (49), whileup to five peaks from hexa-CNs were quantified in pike,burbot, herring, cod, and guillemot from the Baltic Sea (34).PCNs 66/67 together with one unidentified and lesscontributing hexa-CN were found in adipose tissue ofCanadians (36).

In this study, depending on the sample type, PCNs 66/67 and 69, alone or in combination, and in some cases alsoPCNs 71/72 were the most abundant hexa-CNs (Figure 4).There is only a rough compositional similarity in the pattern

VOL. 30, NO. 11, 1996 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3273

+ +

+ +

of hexa-CNs for such environmental matrices as plankton,lesser sand eel, sand eel, stickleback, and sediment. For allother biota samples, the pattern of hexa-CNs variesmarkedly (Figure 4). The composition of hexa-CNs inHalowax 1014 is also quite different from that in sedimentand biological samples.

PCNs 66/67 are highly dominating constituents amongthe isomers of hexa-CN in the plankton sample examined.That finding, if considering that subsurface marine planktonreflects well the composition of hexachloronaphthalenesdeposited from the air, can imply that physical and chemicalproperties of PCNs 66/67 highly favor their selective releasefrom the land-based sources and their prevalence in theatmosphere. PCNs 66/67 are highly dominating membersin the hexa-CN homologue group in exhaust gas from theMSW incinerator (22).

Heptachloronaphthalenes. PCNs 73 and 74 togetherwith octa-CN (OCN; PCN 75) are the largest moleculesamong the PCNs. These two hexa-CNs were found insurface sediment and all biota samples examined, whichindicates their permeability throughout biological mem-branes and their bioaccumulation potential in exposedmarine animals. Nevertheless, the concentrations as wellas contributions from hepta-CNs to the total PCNs wererelatively low in all biota and surface sediment samples(Table 1).

Altogether up to 44 of 48 possible congeners of tetra-throught hepta-CN could be quantified in riverine surfacesediment and in marine animals. The patterns of PCNsfound are matrix dependent and seem to reflect both ahigher environmental mobility of relatively lower chlori-nated tetra- and penta-CNs on one side, and an organism-specific metabolic breakdown possibility and structure-related persistency of some of the chloronaphthalenes onthe other.

AcknowledgmentsThis research was supported by the Statens Naturvårdsverk,Sweden (under the Valfrid Paulsson’s Visiting ProfessorFellowship award to J. F.) and the University of Umea, andpartly by the Polish Committee of Scientific Research (KBN)under Grant C/2359/95sSzwecja and DS. We are gratefulto Dr. L. Oberg for a critical reading of the manuscript.

Literature Cited(1) Mitten, M. E.; Dress, K. S.; Krochta, W. G.; Ewald, F. P.; De Witi,

B. J. In Encyclopedia of Industrial Chemical Analysis; John Wileyand Sons Inc.: New York, 1970; Chapter 9, pp 369-410.

(2) Opperhuizen, A. Toxicol. Environ. Chem. 1987, 15, 249-264.(3) Isnard, O.; Lambert, S. Chemosphere 1988, 10, 440-448.(4) Crookes, M. J.; Howe, P. D. Environmental hazard assessment:

halogenated naphthalenes; TSD/AD, Department of the Envir-onment: London, Great Britain, 1993.

(5) Asplund, L.; Jansson, B.; Sundstrom, G.; Brandt, L.; Brinkman,U. A. Th. Chemosphere 1986, 15, 619-628.

(6) Falandysz, J.; Strandberg, L.; Kulp, S. E.; Strandberg, B.; Bergqvist,P.-A.; Rappe, C. Chemosphere 1996, 33, 51-69.

(7) Falandysz, J.; Rappe, C. Environ. Sci. Technol., in press.(8) Kirk-Othmer. Encyklopedia of Chemical Technology; John Wiley

and Sons Inc.: New York, 1980.(9) Ofstad, E. B.; Lunde, G.; Martinsen, K.; Rygg, B. Sci. Total Environ.

1978, 10, 219-230.(10) Bergman, A.; Hagman, A.; Jacobsson, S.; Jansson,B.; Ahlman, M.

Chemosphere 1984, 13, 237-250.(11) Shiraishi, H.; Pilkington, N. H.; Otsuki, A.; Fuwa, K. Environ. Sci.

Technol. 1985, 19, 585-590.(12) Vogelgesang, J. Z. Wasser-Abwasser-Forsch. 1986, 19, 140-144.(13) Yasuhara, A.; Morita, M. Environ. Sci. Technol. 1988, 22, 646-

650.

(14) Oehme, M.; Mano, S.; Mikalsen, A. Chemosphere 1987, 16, 143-153.

(15) Erikson, M. D.; Swansos, S. E.; Flora, J. D.; Hinshaw, G. D. Environ.Sci. Technol. 1989, 23, 462-470.

(16) Benfenati, E.; Mariani, G.; Fanelli, R.; Zuccotti, S. Chemosphere1991, 22, 1045-1052.

(17) Wiedmann, T.; Ballschmiter, K. Organohalogen Compd. 1992,9, 331-324.

(18) Nakano, T.; Fujimori, K.; Takaishi, Y.; Umeda, H. Rep. HyogoPrefect. Inst. Environ. Sci. 1993, 25, 33-40.

(19) Imagawa,T.; Yamashita, N.; Miyazaki, A. J. Environ. Chem. 1993,3, 221-230.

(20) Wiedmann, T.; Ballschmiter, K. Fresenius J. Anal. Chem. 1993,346, 800-804.

(21) Haglund, P.; Jakobsson, E.; Asplund, E.; Athanasiadou, M.;Bergman, A. J. Chromatogr. 1993, 634, 79-86.

(22) Takasuga, T.; Inoue, T.; Ohl, E.; Ireland, P. Organohalogen Compd.1994, 19, 177-182.

(23) Imagawa, T.; Yamashita, N. Organohalogen Compd. 1994, 19,215-218.

(24) Haglund, P.; Jakobsson, E.; Masuda, Y. Organohalogen Compd.1995, 26, 405-410.

(25) Halowax, Chlorinated Naphthalene Oils and Waxlike Solids;Koppers Chemicals and Coatings, undated brochure.

(26) Brinkman, U. A. Th,; Reymer, H. G. M. J. Chromatogr. 1976, 127,203-243.

(27) Falandysz, J. Farm. Pol. 1981, 37, 125-131.(28) Falandysz, J.; Yamashita, N.; Tanabe, S.; Tatsukawa, R. Int. J.

Environ. Anal. Chem. 1992, 47, 129-136.(29) Beland, F. A.; Geer, R. D. J. Chromatogr. 1973, 84, 59-68.(30) Bletchly, J. D. In PCB Seminar; Barres, M. C., Koeman, H., Visser,

R., Eds.; Ministry of Housing, Physical Planning, and Environ-ment: Amsterdam, 1994; pp 343-372.

(31) Voogt de, P.; Brinkman, U. A. Th. In Halogenated Biphenyls,Terphenyls, Naphthalenes, Dibenzodioxins and Related Products;Kimbrough, R. D., Jensen, A. A., Eds.; Elsevier: Amsterdam, 1989;pp 1-45.

(32) Chemical formulations for preservation of wood; Instytut TechnikiBudowlanej: Warszawa, undated brochure; pp 5-7 (in Polish).

(33) Jakobsson, E. Ph.D. Dissertation, Stockholm University, 1994.(34) Campbell, N. In Rodd’s Chemistry of Carbon Compounds Vol. III

Part G.; Coffey, G., Ed.; Elsevier: Amsterdam, 1978; p 99.(35) Jarnberg, U.; Asplund, L.; de Wit, C.; Grafstrom, A.-K.; Haglund.

P.; Jansson, B.; Lexen, K.; Strandell, M.; Olsson, M.; Jonsson, B.Environ. Sci. Technol. 1993, 27, 1364-1374.

(36) Williams, D. T.; Kennedy, B.; LeBel, G. L. Chemosphere 1993, 27,795-806.

(37) Asplund, L.; Jakobsson, E.; Haglund, P.; Bergman, A° . Chemosphere1994, 28, 2075-2086.

(38) Schlabach, M.; Biseth, A.; Gundersen, H.; Knutzen, J. Organo-halogen Compd. 1995, 24, 489-492.

(39) Hanberg, A.; Waern, F.; Asplund, L.; Haglund, E.; Safe, S.Chemosphere 1990, 20, 1161-1164.

(40) Engwall, M.; Brunstrom, B.; Jakobsson, E. Arch. Toxicol. 1994,68, 37-42.

(41) Falandysz, J.; Strandberg, L.; Bergqvist, P.-A.; Strandberg, B.;Rappe, C. Mar. Pollut. Bull., in press.

(42) Bergqvist, P.-A.; Bandh, C.; Broman, D.; Ishaq, R.; Lundgren, K.;Naf, C.; Pettersen, H.; Rappe, C.; Rolff, C.; Strandberg, B.; Zebhur,Y.; Zook, D. Organohalogen Compd. 1992, 9, 17-20.

(43) Huckins, J. N.; Tubergen, M. W.; Lebo, J. A.; Gale, R. W., Schwartz,T. R. J. Assoc. Off. Anal. Chem. 1990, 73, 290-293.

(44) Bergqvist, P.-A.; Strandberg, B.; Bergek, S.; Rappe, C. Organo-halogen Compd. 1993, 11, 41-44.

(45) Lundgren, K.; Bergqvist, P.-A.; Haglund, P.; Rappe, C. Organo-halogen Compd. 1992, 8, 103-106.

(46) Brinkman, U. A. Th.; De Kok, A. In Halogenated biphenyls,terphenyls, naphthalenes, dibenzodioxins and related products;Kimbrough, R. D., Ed.; Elsevier: Amsterdam, 1980; pp 71-102.

(47) Sakai, S.; Hiraoka, M.; Takeda, N.; Shiozaki, K. Bull. Environ.Contam. Toxicol. 1996, 32, 79-88.

(48) Jarnberg, U.; Asplund, L.; Jakobsson, E. J. Chromatogr. 1994,683, 385-396.

(49) Jansson, B.; Asplund, L.; Olsson, M. Chemosphere 1984, 13, 33-41.

Received for review January 19, 1996. Revised manuscriptreceived June 8, 1996. Accepted June 11, 1996.X

ES960057E

X Abstract published in Advance ACS Abstracts, September 1, 1996.

3274 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 30, NO. 11, 1996

+ +

+ +