Polychlorinated naphthalenes in three-spined stickleback Gasterosteus aculeatus from the gulf of Gdańsk

Chemosphere, Vol. 37, Nos 9-12, pp. 2473-2487, 1998 0 1998 Elsevier Science Ltd All rights reserved. Printed in Great Britain 0045-6535198 $19.00+0.00

PII: SO0456535(97)10241-7

POLYCHLORINATED

NAPHTHALENES

IN THREE-SPINED

STICKLEBACK

GASTEROSTEUS ACULEATUS FROM THE GULF OF GDAfiSK

Jet-q Falandysz*, Lidia Strandberg*, Bo Strandberg ** and Christoffer Rappe**

*Department of Environmental Chemistry & Ecotoxicology, University of Gdtisk,

PL 80-952 Gdtisk, Poland

**Institute of Environmental Chemistry, Ume& University, S-901 87 Umel, Sweden

ABSTRACT

The congener-specific data of polychlorinated stickleback collected>om

naphthalenes (PCNs) are presented for the three-spined

four spatially distant sites in the beach zone in the south-western part of the Gulf oj

Gdarisk, Baltic Sea. The lipid weight normalised concentration of total PCNs in stickleback ranged from 35 to 130 rig/g.. Tetra-CNs (54-64%) were a dominating chloronaphthalene homologue group in sticklebacks, followed by penta- (37-44%), hexa- (0.9-1.7%), and hepta-CNs (0.02-~0.1%). congeners showed the 1,2,3,5,7-/1,2,4,6,7-PSCN

The fingerprint

(Nos 52/60), 1,2,4,6-/1,2,4,7-/1,2,5,7-T4CN

1,3,5,7-T4CN (No. 42) as a most contributing members, and also some compositional patterns of tetra-. penta-, and hexa-CNs displayed compositional

of chloronaphthalene (Nos 33/34/37) and (%) differences. The

variations in a residue picture of those

substances, depending on the sampling site, and implied on a specific point source of pollution, possibly due to the neighbourhood of shipyards and marine ports, as a cause of the dlflerences/similarities

observed.

01998 Eisevier Science Ltd. AN rights reserved

Key words: Chloronaphthalenes,

CNs, Polychlorinated

stickleback, pollution, Baltic Sea.

2473

naphthalenes,

PCNs, HRGCYHRMS, analysis,

fish,

2414 INTRODUCTION

Polychlorinated

naphthalenes (PCNs) form a complex mixture of 75 congeners of different physical and

chemical properties, and also of different environmental

stability and biological activity (Hanberg et ~1. 1990;

Engwall et al. 1994; Jakobsson 1994; Falandysz 1997; Falandysz and Rappe, 1996 and 1997; Falandysz L’Ial. 1996a,b and 1997a,b). The sources of environmental pollution with PCNs can be attributed to the technical PCN formulations (Halowax, Nibren Waxs, Seekay Waxes, Clonacire Waxes, etc.) itself and products containing those substances,

and also to the thermal or other reactions

in the presence

incineration, copper roasting, aluminium smelting erc.) (Falandysz Attiola et al. 1994; Jakobsson

of chlorine

(municipal

solid waste

1981; Wiedmann and Ballschmiter.

1993;

1994; Imagawa and Yamashita, 1994; Takasuga et al. 1994; Sakai Ed al. 1996;

Schneider et al. 1996). The technical polychlorinated

naphthalene formulations show a high degree of similarity

in their properties and appliances to the technical polychlorinated

biphenyls (PCBs), and also the restrictions on

the production and use of PCN mixtures seem to follow the pattern generally known to PCBs. Nevertheless, some technical products and processes still can be the sources of environmental contamination with PCNs (Weistrand et al. 1992; Popp et al. 1993; Jan et al. 1994). Here we examine, if there exist any differences

or similarities in spatial distribution

fingerprint and pattern of pollution with PCNs in a beach zone in the south-western (Figure I), using the three-spined

sticklebacks

part of the Gulf of Gdar’rsk

(Gasterosteus aculleatus) as a biological

destructive extraction and clean-up method coupled to a HRGUHRMS

in concentration,

matrix and a non-

technique.

MATERIALS AND METHODS

30 male and female adults of the three-spined sticklebacks (Gasterosteus aculeatus) were collected at four sites in the beach zone in the south-western part of the Gulf of Gdansk from June 2 to July 1, 1992 (Figure 1). The analytical method used for determination of chloronaphthalenes allowing to determine

simultaneously

many organochlorines

(Bergqvist et al., 1992). After homogenisation

is a part of a multi-residue procedure

and polynuclear

aromatic hydrocarbons

(PAH)

of the sample containing 30 whole individuals (145310.6 g) with

anhydrous sodium sulphate (1:7; baked at 550°C for 2 days), the powdered mixture was packed into a wide bore open glass column, spiked with an internal standard (“C,, - 3,3’,4,4’,5-pentachlorobiphenyl;

PCB 126), extracted

with 500 ml of a mixture of acetone and n-hexane (2.5: 1) followed by 500 ml of n-hexane and diethyl ether (9: l), to obtain a fat extract. The solvents were carefully evaporated on a water bath under vacuum pressure, using a rotary evaporator. Then, pure ethanol was added, to remove azeotropically co-extracted water, also under vacuum

2475

The Gulf of Gdatisk

T

Redlowo

Figure 1. Sampling sites (*) of sticklebacks.

and using rotary evaporator.

Bulk lipid removal was performed by means of the polyethylene

film dialysis

method (Bergqvist et al., 1993; Huckins et al., 1990). After dissolving the extracted lipids in cyclopentane. dialysis through the polymeric membrane was accomplished by changing the dialysate after 24, 48 and 72 hours The three dialysate fractions, containing normally between I - 10% of the original lipids, depending on sample size and matrix type, were combined and concentrated to a few millilitres using a rotary evaporator. The extract was split into two parts, of which 90% was used for analysis of PCNs and some other planar compounds not described here, while 10% was used for the analysis of organochlorine pesticides and PCBs. The remaining fat was removed on a combined column packed as follows from the bottom: glass wool, 10 ml potassium silica, a layer of neutral silica gel (1 g), 20 ml 40% sulphur acid silica gel, 10 ml 20% sulphuric acid silica gel, 20 ml neutral silica and a layer of sodium sulphate. The column length was 20 cm and the diameter was 38 mm. The gravimetric elution 01’ planar organochlorines

was done with 200 ml of n-hexane and 40 ~1 of tetradecane was added as a keeper before

evaporation of the solvent. The extract was then fractionated by HPLC using an activated carbon column (Amoco PX-2; 2-l 0 ,KIII,dispersed on LiChrospher RF’-18; 15-25~)

(Lundgren et al., 1992). Between the carbon column

and the pre-column a filter valve (Valco Instruments Co. Inc., TX, US), was mounted enabling a backflush of the column. The elution

from the HPLC carbon

column

was performed

with

1% methylene

chloride

in n-hexane

FOI

2476 7.5 minutes (solvent I), and then a gradient up to 10% toluene in n-hexane within 32.5 minutes (solvent 2) Solvents were of high purity grade (Burdick and Jackson, Muskegon, MI, US) and degassed with argon. Fraction one containing organochlorine

pesticides and 2-4 orrho PCBs. was collected during the first 15 minutes and

fraction two, containing mono-o&to

PCBs, between 15 and 40 minutes. The total volume of solvents used was

160 ml, and the flow rate was 4 ml per min. PCNs together with PCDDs, PCDFs and non-ortho planar PCBs were eluted by backflush with 80 ml of toluene. The eluate was concentrated pentachlorobiphenyl

and spiked with “C,,-2,2’.4.5.5’-

(PCB no. 101) as recovery standard and evaporated to a final volume 30 /II after adding

tetradecane as a keeper. A gas chromatograph

(Hewlett Packard 5890 GC) coupled to a high resolution mass spectrometer (VG

Analytical 1 l-250 J, Altrincham, United Kingdom) was used for the determination of PCN congeners. The mass resolution of the mass spectrometer (MS) was 8 000 amu, and the calibration gas was perfluorokerosone Injections were made in the splitless mode and the oven was temperature

programmed

(PFK).

as follows: initial

temperature 18O”C, initial time 2 min, 20”Clmin to 200°C then 4OC/min to 300°C (isothermal for 15 min). A Rtx-5 fused silica capillary column (60 m x 0.32 mm i.d.), coated with crossbond 5% diphenyl - 95% dimethyl polysiloxane with a film thickness of 0.25 F

was employed for the analysis. The ion source was kept at 250°C

and operated under electron impact (EI) conditions at 70eV, and the MS was tuned in the selected ion recording (SIR) mode. For the confirmation/quantification

of PCNs the two most abundant ions in the chlorine cluster of the

molecular ion were monitored at m/z 263..9 and 265.9 for tetra-CNs, m/z 297.9 and 299.9 for penta-CNs, m/z 331.8 and 333.8 for hexa-CNs, and m/z 365.8 and 367.8 for hepta-CNs. The 13C- labelled PCBs 126 (internal standard) and 101 (recovery standard) were used to compensate for possible losses during the clean-up procedure. A procedural blank was performed

with the every set of real samples examined.

The technical mixture of

Halowax 1014 was used to determine the elution order and pattern of PCNs in the sample chromatograms. Appropriate chromatographic data published for Halowax 1014 by Wiedmatm and Balls&miter (1993), Nakano et al. (1993), Takasuga er al. (1994), and Imagawa & Yamashita (1994) were used to identify the elution pattern of tetra-

to hexa-CNs

(hexachloronaphthalenes

on the

Rtx-5

capillary

coh.trnn. PCN

and heptachloronaphthalene,

nos.

respectively

66/67

and

- synthesized

71 as well

as no. 73

by Dr. Eva Jakobsson,

Stockholm University) were used for quantification by peak area. The hexa- and hepta-CNs were quantified on the basis of the molar response (MR) factors of congeners nos. 66167, 71 and 73, respectively.

Since standards for

individual native mono- through penta-CNs or their “Cn - labeled analogues were not available, the MR (SIM) factors of hexa-CNs were used to quantify the tetra- and penta-CNs by corrections for the differences ionization cross-section

(Q), which is 33.7, 36.9 and

respectively (Wiedmann & Balls&miter,

1993).

in the

40.1~10~‘~ cm* for the tetra-, penta- and hexa-CNs,

2477 RESULTS AND DISCUSSION

Many tetra- through hepta-CNs were found in sticklebacks (Table 1). The Westerplatte (Port Polnocny) and Oksywie sampling port/navy/shipyards

sites are localated close to the sea arbour (city of Gdarisk) and of a complex of

activities (city of Gdynia), respectively, while the sites Gorki Zachodnie and Redkowo are

relatively distant from direct point sources of possible pollution by industrial organohalogens. The lipid weight normalised total PCN concentration is comparable at the Gorki Zachodnie, Westerplatte and Oksywie sampling sites, while it is much lower at the Redlowo site (Table 1). In a study by Holm et al. (1993) the uptake efficiency concentrations

of Halowax

1014 given to sticklebacks

in

of 65&l and 97+11 pg per gram of feed was ca. 20%, and the amount of PCNs bioaccumulated

was 845+43 and 1929*72 ,&g lipid weight, respectively.

Fingerprint

In sticklebacks from the all sampling sites (Fig. I), like in many other species of fish and other organisms from the southern part of the Baltic Sea (Falandysz et al. 1996ab, 1997ab), the tetra- (56-64%) and penta-CNs (37-44%) are usually dominating and hexa- and hepta-CNs are only minor compounds (from 0.9 to 1.7 and from 0.02 to below O.l%, respectively). The chloronaphthalene technical PCN formulations

homologue

group composition

is roughly known for all of the USA produced

of the Halowax series (Jakobsson

1994), and it is assumed that technical PCN

formulations produced in other countries has the same homologue group composition. The exact amount of PCN produced world-wide is estimated to 150 000 metric tones. However no specific man factoring data are available. Data about homologue

group composition

of chloronaphthalenes

formed during municipal solid waste

combustion and other thermal processes (Benfenati et al. 1991; Aittola et al. 1994; Sakai et al. 1996; Schneider et al. 1996) indicate, that their concentrations decrease in the order: tetra - and penta-CNs >> hexa- and tri-CNs 7 diCNs 77 mono- and hepta-CNs 7 octachloronaphthalene. The amount of PCNs released to the environment due to thermal formation and by other processes where chlorine is present is assessed to be 1- 10 metric tones in this century (Falandysz, 1997), what is much less than the 150 000 tones synthesized or the 100 tones present as impurities in technical polychlorinated

biphenyl (PCBs)

formulations. A relatively higher vapour pressure of tetra- and penta-CNs (estimated value of 3.2 x 1Oe5- 3.6 x 10. 4 mm Hg) when compared to higher chlorinated members (Crookes and Howe, 1993), and in parallel a difference in water solubility w-ill favour a higher environmental mobility of mono- to penta-CNs than hexa- to octa-CN.

2478 Table I. Polychlorinated naphthalenes in sticklebacks (rig/g lipid wt) from the Gulf of Gdansk

PCN no. Structure Tetrachloronaphthalenes 42 1,3.5,7-T&N 33134137 1.2,4,6-11,2,4,7-/1,2,5,7-T,CN 44 I ,3,6,7-T&N 47 I .4,6,7-T&N 36145 1,2,5,6-/1,3,6,8-T&N 28143 1,2,3,5-/1,3,5,8-T,CN 27/30/39 1,2,3,4-11,2,3,7-/1,2,6,7-T&N 32148 1,2,4,5-/2,3,6,7-T&N 35 1,2,4,8-T,CN 38/40 I ,2,5,8-/l ,2,6,8-T&N 46 1,4,5,8-T&N 41 1,2,7,8-T&N Total tetra-CNs Pentachloronaphthalenes 52J60 1,2,3,5,7-/1,2,4,6,7-P,CN 58 1,2,4,5,7-P,CN 61 1,2,4,6,8-P&N 50 1,2,3,4,6-P,CN 51 1,2,3,5,6-P&N 54 1,2,3,6,7-P,CN 57 1,2,4,5,6-P,CN 62 1,2,4,7,8-P,CN 53155 1,2,3,5,8-/1,2,3,6,8-P,CN 59 1,2,4,5,8-P&N 49 1,2,3,4,5-P&N 56 1,2,3,7,8-P&N Total penta-CNs Hexachloronaphthalenes 66167 1>,,,, 2 3 4 6 7-A 1,))) 2 3 5 6 7-H&N 64168 1,2,3,4,5,7-/l ,2 >3 75 ,6 7I-H&N 69 1,2,3,5,7,8-H,CN 71172 1,2,4,5,6,8-/1,2,4,5,7,8-H&N 63 1,2,3,4,5,6-H&N 65 1,2,3,4,5,8-H&N Total hexa-CNs Heptachloronaphthalenes 73 1,2,3,4,5,6,7-H&N 74 1,2,3,4,5,6,8-H,CN Total hepta-CNs Total PCNs

Sampling site and date, and lipid content (%) Gorki Zachodnie Westerplatte Redlowo June 2, 1992 July I, 1992 June 3, 1992 2.44 (%) 2.66 2.38

Gksywie June 15, 1992 2.44

15 15 0.58 6.6 0.71 6.2 1.1 0.92 3.9 3.5 1.6 0.16 56

14 17 0.46 5.6 0.67 7.2 1.2 0.83 5.3 4.8 2.7 0.20 60

4.9 5.5 0.23 2.6 0.24 2.3 0.39 0.29 1.4 1.4 0.62 0.059 20

8.2 1.3 I.5 8.5 6.0 4.2 0.37 70

18 1.1 4.4 0.88 0.65 0.48 2.2 1.5 1.1 1.1 0.14 0.044 32

16 1.4 6.4 1.5 0.79 0.24 3.1 3.6 1.5 1.8 0.21 0.10 37

8.4 0.35 1.7 0.61 0.41 0.27 0.94 0.80 0.59 0.40 0.076 0.028 15

21 1.7 12 1.7 0.94 0.37 6.1 6.2 2.8 4.5 0.44 0.13 57

0.45 0.096 0.13 0.062 0.044 0.011 0.79

0.40 0.22 0.35 0.19 0.12 0.063 1.3

0.37 0.058 0.082 0.032 0.026 0.015 0.58

0.59 0.30 0.47 0.29 0.14 0.096 1.9

0.0032 0.004 0.0072 88

0.013 0.0081 0.021 98

0.007 0.004 0.011 35

0.030 0.017 0.047 130

13 20 0.35 6.2 0.59

No. 74b!_

_

No.47h/ I Nos 36145 Nos 28143 Nos 27130139 Nos 32148 No. 35 Nos 38/40 No. 46 No. 41 Nos 52/60 No. 58 / No. 61 No. 50 No. 514 No. 541 j : 1 No. 57 No.62 Nos 53155 No. 59 No. 49 No. 56 Nos 66167 Nos 64/68

1:

2480

There arc only a few dominating

tetra- through hepta-CN congeners

sticklebacks (Figure 2), and similar patterns were

observed

present in the fingerprint of rn

in some other fish species examined (Falandysz e/ trl.

I997 ab). 1,2,3,5,7-11,2.4,6,7-P&N

(Nos 52160). 1,2,4,6-/1,2,4,7-/1,2,5,7-T,CN

(Nos 33134137) and 1,3.5,7-T,CN

(No 42) are the most abundant (-10 - -20% of the quantified PCNs) in sticklebacks (Figure 2). Some other PCN congeners such as 1,4,6,7-T&N (No. 47), 1,2,3,5-/1,3,5,8-T,CN (Nos 28/43), 1,2,4,8-T,CN

(no.

35)

and

1.2,4.6.8-

P&N (No. 61) has an abundance > 5%, and for 1,2,5,8-/1,2,6,8-T,CN (Nos 38140) is -5% (Figure 2). Selected penta-CNs (Nos 57, 62, 53/55 and 59) showed higher abundance and a similar concentration pattern in sticklebacks sampled at the Oksywie and Westerplatte sites. Those penta-CNs such as (Nos 57, 62. 53155 and 59) are a dominating members in the compositional pattern of technical Halowax 1014 (Figure 2).

Patterns

Compositional

differences

in the level of tetra-, penta- and hexa-CNs in stickleback from the different

sampling sites were also studied. The patterns of some homologue groups are shown in Figures 3-5. There are a small differences in the tetra-CNs patterns of stickleback collected at the Gorki Zachodnie and Redlowo sampling sites vis. those from the Westerplatte (Port Polnocny) and Oksywie (Figure 3) (Falandysz er al. 1996~). All found tetra-CNs patterns are totally different to that formed for Halowax 1014 (Figure 2) or EquiHalowax (an equivalent mixture of all types of the technical Halowax formulations)

(Imagawa and Yamashia,

1994; Takasuga er al. 1994). A striking difference in the pattern of tetra-CNs in stickleback compared to Halowax 1014 (Figure 2), Equi-Halowax and thermal formation (Imagawa and Yamashita, 1994; Talcasuga et al. 1994) is the relatively high abundance of 1,3,5,7-T&N (No. 42). This is the only tetra-CN isomer, where all vicinal carbon atoms are substituted biomagnification

with chlorine.

This particular isomer has relatively high bioaccumulation

(BAF) and

(BMF) factors in many fish species, in black cormorant and white-tailed sea eagle (Falandysz

1997; Falandysz et al. 1997 b). Therefore, the relatively high abundance of 1,3,5,7-T&N (No. 42) in stickleback seems to be due to its environmental persistency and not caused by a special source. 1,3,6,7-T&N (No. 44), a congener which is absent in technical PCNs of the Halowax series but formed in thermal processes (Takasuga ef al. 1994), was found in sticklebacks from all sampling sites (Table 1). Therefore, apart from technical PCN mixtures, the formation of PCN by thermal processes results in an environmental burden of the Gulf of Gda+.k. Compared to tetra-CNs, the pattern both of penta- (Figure 4) and hexa-CNs (Figure 5) exhibit more pronounced and site specific differences.

The penta-CNs patterns in stickleback from Oksywie and Westerplatte

were different from those at Redlowo and Gorki Zachodnie (Figure 4).

2481 !,@

1 ,;a i T A -

I

I33134137 I

Oksywie

42

',:! *-

t [min]

Redlowo

t [min] Figure 3. HRGC-MS/F&SIR chromatograms (Rx-S) of tetrachloronaphthalenes in sticklebacks collected at the Oksywie and Red!owo sampling sites (ion mass: 263.9).

2482

t [min]

Figure 4. HRGC-MS/El-SIR chromatograms (RX-~) of pentachloronaphthalenes in sticklebacks collected at the Oksywie and Redlowo sampling sites (ion mass: 297.9).

2483

66 67

69

Red lowo

65

Figure 5. HRGC-MS/El-SIR chromatograms (Rx-5) of hexachloronaphthalenes in sticklebacks collected at the Oksywie and Rediowo sampling sites (ion mass: 33 1.8).

2484 I ,2,3,5,7-/l ,2,4,6,7-P&N

(Nos 52/60) and I ,2,4,6,8-P,CN (No. 61) arc most abundant at all the sampling

sites (Table I). These isomers including 1,2,4,5,7-P&N

I .3,5,7-T&N

(No. 58) have unsubstituted

(No. 42). All these penta-CNs are relatively highly bioaccumulated

vicinal carbon atoms like and biomagnified

by fish.

marine birds and birds of prey. Some other penta-CNs where two vicinal carbon atoms are unsubstituted with chlorine on one or both naphthalene

nuclei (DVC-Cl) are also enriched (Falandysz

1997). 1.2,3.5.7-/1.2,4.6,7-

P&N (Nos 52160) are the most abundant isomers formed in thermal processes, and minor constituents (- 5%) in Halowax 1014 and Equi-Halowax (Figure 2) (Imagawa and Yamashita, 1994; Takasuga et ul. 1994). The DVC-Cl PCNs nos 57,62,53/55 and in Equi-Halowax,

and 59 are the most abundant penta-CN isomers in Halowax (Fig. 2)

but only in minor amounts formed during thermal processes

A relatively higher level

(Takasuga ef al. 1994).

of nos 57, 62, 53/55 and 59 in stickleback from Oksywie and Westerplatte when

compared to Redlowo and Gorki Zachodnie seems to indicate the existence of a local pollution source of technical PCN at the first ones. The patterns of hexa-CNs were similar in stickleback from Oksywie and Westerplatte and differed largely from that for Redtowo and Gorki Zachodnie sites (Figure 5). Hexachloronaphthalenes

compared to tetra- and

penta-CNs are less water soluble and volatile, and have higher Log Kow and Log KAC values (Crookes and Howe, 1993). Hexa- and more chlorinated congeners of naphthalene due to mentioned physicochemical

properties

can be relatively less mobile in the environment when compared to their lower chlorinated analogues. and so with longer residence time close to a point source of pollution. The most abundant among of hexa-CNs in sticklebacks are 1,2,3,4,6,7-/1,2,3,5,6,7-H&N(Nos 66167). Those isomers are very persistent in the environment (Jakobsson 1994; Falandysz and Rappe, 1996), and are the most abundant isomers of hexachloronaphthalene

formed during

thermal processes and minor in Halowax 1014 and Equi-Halowax (Imagawa and Yamashita, 1994; Takasuga et

al. 1994). Concluding, a site dependent

differences/similarities

in the patterns of tetra-, penta- and hexa-CNs in

sticklebacks (Figures 3-5) seem to indicate on existence of the local source of pollution with technical PCNs at the Oksywie and Westerplatte (Port Polnocny) sites in the Gulf of Gdansk. Due to detection of 1,3,6,7-T,CN (No 44)) in stickleback, i.e. a congener which is formed during thermal processes and is absent in technical formulations of the Halowax series, a wide-spread

background pollution with PCNs because of combustion seems to be also a

matter of concern for the further studies.

ACKNOWLEDGMENTS

This research was supported by the Statens Naturvardsverk,

Sweden (under the Valfiid Paulsson Visiting

Professor Fellowship award to Prof. J. Falandysz) and partly by the Polish Committee of Scientific Research (KBN) under grant DS.

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