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Chemosphere 70 (2008) 1552–1562

Occurrence of polychlorinated naphthalenes, polychlorinatedbiphenyls and short-chain chlorinated paraffins in marine

sediments from Barcelona (Spain)

P. Castells, J. Parera, F.J. Santos *, M.T. Galceran

Departament de Quımica Analıtica, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain

Received 18 April 2007; received in revised form 17 August 2007; accepted 17 August 2007Available online 29 October 2007

Abstract

Polychlorinated naphthalenes (PCNs), short-chain chlorinated paraffins (SCCPs) and polychlorinated biphenyls (PCBs) were ana-lysed in marine sediment samples collected from the coastal area of Barcelona (Spain) and near of a submarine emissary coming froma waste water treatment plant located at the mouth of the Besos River (Barcelona). An integrated sample treatment based on Soxhletextraction followed by a simple clean-up with Florisil and graphitized carbon cartridge was employed. Gas chromatography coupled toion-trap tandem mass spectrometry (GC–MS/MS) and gas chromatography–mass spectrometry in electron capture negative ionizationmode, were used for PCN and SCCP determinations, respectively, while for PCB analysis gas chromatography with electron capturedetection (GC-ECD) was used. The method developed provided low limits of detection (0.001–0.003 ng g�1 dry weight (dw) for PCNs,1.8 ng g�1 for SCCPs and 0.006–0.014 ng g�1 dw for PCBs) and good run-to-run precisions (lower than RSD 8%) for the analysis ofsediment samples. Concentration levels ranging from 0.17 to 3.27 ng g�1 dw for PCNs, between 0.21 and 1.17 lg g�1 dw for SCCPs,and from 2.33 to 44.00 ng g�1 (dw) for PCBs, were found in the coastal sediments, while for samples collected near to the submarineemissary higher levels (from 2.02 to 6.56 ng g�1 dw for PCNs, between 1.25 and 2.09 lg g�1 dw for SCCPs and from 22.34 to37.74 ng g�1 dw for PCBs) were obtained. The results obtained provide new data about the occurrence of PCN and SCCP in the coastalarea of Barcelona.� 2007 Elsevier Ltd. All rights reserved.

Keywords: Sediments; Environmental analysis; Mass spectrometry; Polychlorinated naphthalenes; Polychlorinated biphenyls; Chlorinated paraffins

1. Introduction

Persistent organohalogen compounds such as polychlo-rinated naphthalenes (PCNs), chlorinated paraffins (CPs)and polychlorinated biphenyls (PCBs) are well-knownenvironmental contaminants. These three classes of com-pounds are ubiquitous global pollutants which can be oftenfound in different environmental compartments, althoughtheir use and production has been restricted (CPs) orbanned (PCBs and PCNs). Since physical properties and

0045-6535/$ - see front matter � 2007 Elsevier Ltd. All rights reserved.

doi:10.1016/j.chemosphere.2007.08.034

* Corresponding author. Tel.: +34 934034874; fax: +34 934021233.E-mail address: javier.santos@ub.edu (F.J. Santos).

chemical structures of PCNs and PCBs are similar theyhave been used in similar applications, such as dielectricfluids, insulators, additives and preservatives. Chlorinatedparaffins (CPs) are complex mixtures containing a verylarge number of individual isomers (Tomy et al., 1997;Shojania, 1999) which are particularly good PCN andPCB substitutes in a wide variety of industrial applications.In fact, world production of short-chain CPs (C10–C13 CPs,SCCPs) has increased after the banning of PCNs andPCBs. As recognised persistent organic pollutants (POPs),these compounds are frequently detected in a wide varietyof environmental matrices such as sediments, soils, water,biota and air, in both industrial and non-industrial areas(Coelhan, 1999; Eljarrat et al., 1999; Tomy et al.,

P. Castells et al. / Chemosphere 70 (2008) 1552–1562 1553

1999a,b; Yamashita et al., 2000a,b; Nicholls et al., 2001;Castells et al., 2003; Harner et al., 2006; Manodori et al.,2006), although SCCPs are not found in air because oftheir low vapour pressures (Peters et al., 2000). Generally,PCNs, PCBs and SCCPs have been mainly released intothe environment due improper use and disposal afterintended production, although PCNs can also be releasedfrom municipal solid waste incinerators (MSWIs) andsome other industrial processes (Abad et al., 1999).

Toxicity of PCNs and PCBs has been extensivelyreported in the literature (Falandysz, 1998, 2003; Hayward,1998; Villeneuve et al., 2000; Brack et al., 2003; Perssonet al., 2005; Yusa et al., 2006; Sprovieri et al., 2007). AllPCN congeners and also non-ortho and mono-ortho-PCBsare more or less planar compounds, and carcinogenic riskderived from the exposure to such kind of pollutants is alsowell-known. Non-ortho and mono-ortho-PCBs exhibitdioxin-like toxicity, and several hexachlorinated naphtha-lenes (such as 1,2,3,4,6,7-hexaCN and 1,2,3,5,6,7-hexaCN)and 1,2,3,4,5,6,7-heptaCN have a toxic equivalency factorsimilar to mono-ortho-PCBs (Engwall et al., 1994; Falan-dysz and Puzyn, 2004), which is 0.001 relative to 2,3,7,8-tetrachlorodibenzodioxin (2,3,7,8-TCDD). More recently,and despite their different structures and toxicity mecha-nisms, SCCPs with an average carbon chain length of C12

and 60% of chlorine content have also been included bythe International Agency for Research on Cancer (IARC,1990) in Group 2B as being possibly carcinogenic to

humans. Therefore, several international organisationshave listed SCCPs as substances requiring priority actionand regulation as for PCBs and PCNs (EPA, 1991; CEPA,1993; OSPAR, 1999).

Analysis of SCCPs, PCBs and PCNs is currently per-formed by gas chromatography (GC) coupled to high orlow resolution mass spectrometry (MS) and electron ioni-sation (EI) is commonly used for the congener-specificdetermination of PCNs and PCBs (Kannan et al., 1998;Lunden and Noren, 1998; Yamashita et al., 2000a,b; Lund-gren et al., 2002; Falandysz, 2003; Wang et al., 2005, 2007;Manodori et al., 2006; Pan et al., 2007). However, under EIconditions SCCPs, which are much more labile com-pounds, have shown a high degree of fragmentation (Cas-tells et al., 2004a,b), and for this reason a softer ionisationtechnique such as electron capture negative ionisation(ECNI) in both high and low resolution MS is currentlyused (Coelhan, 1999; Tomy et al., 1999b; Nicholls et al.,2001; Nilsson et al., 2001; Zencak et al., 2004; Brauneet al., 2005; Huittig and Oehme, 2005; Iino et al., 2005;Reth et al., 2005; Stejnarova et al., 2005; Huttig andOehme, 2006). PCNs have also been successfully deter-mined using GC–ECNI-MS (Meijer et al., 2001; Egebacket al., 2004; Carrizo and Grimalt, 2006) but, unfortunately,for CPs no congener-specific determination can be accom-plished due to the huge number of isomers present in thesemixtures. Nevertheless, quantification of the differenthomologue groups of CPs is possible mainly by monitoringtheir corresponding [M�Cl]� ions, although the use of

[HCl2]� and [Cl2]�� ions has also been reported for SCCPdetermination (Nicholls et al., 2001; Castells et al.,2004a,b).

GC–ion-trap tandem mass spectrometry (GC–IT-MS/MS) has been also proposed for the analysis of these com-pounds in several matrices. For instance, PCBs in atmo-spheric particulate samples (Mandalakis et al., 2001),PCNs in biological tissues (Wang et al., 2005, 2007) andsediments (Yusa et al., 2006), and the screening of SCCPsin biological marine samples (Zencak et al., 2004) havebeen performed using this technique providing good selec-tivity and sensitivity at a lower cost than HRMS.

This paper is mainly focused on the determination of theabove mentioned organochlorine compounds (PCNs andSCCPs) in marine sediment samples from a coastal areaof Barcelona (Spain) with the aim of assessing PCN andSCCPs contamination in this area. For this purpose, aGC–IT-MS/MS method was developed for PCN determi-nation while SCCPs were analysed by a GC–ECNI-MSmethod previously developed (Castells et al., 2004b). Inaddition, PCB congeners were also determined in the sedi-ments with the aim of comparing the results with thoseobtained for PCNs and SCCPs and to provide informationabout their presence on this area.

2. Materials and methods

2.1. Standards and reagents

A stock standard solution mixture of eight PCN congen-ers (PCN-MXA) in nonane was obtained from WellingtonLaboratories Inc. (Guelph, Ontario, Canada). This mixturecontained the following PCN congeners at a concentrationof 5.0 lg ml�1: 2-monoCN (PCN-2), 1,5-diCN (PCN-6),1,2,3-triCN (PCN-13), 1,2,3,5-tetraCN (PCN-28), 1,2,3,5,7-pentaCN (PCN-52), 1,2,3,4,6,7-hexaCN (PCN-66),1,2,3,4,5,6,7-heptaCN (PCN-73) and octachloronaphtha-lene (PCN-75). Each PCN congener was representative ofone homologue group. PCN calibration standard solu-tions at concentrations between 0.2 and 300 ng ml�1 wereprepared by dilution of the stock standard solution inisooctane. Halowax 1014 and Halowax 1051 at a concen-tration of 10 lg ml�1 in cyclohexane were purchased fromDr. Ehrenstorfer GmbH (Augsburg, Germany).

A stock standard solution of short-chain chlorinatedparaffin (SCCP C10–C13, 63% Cl) in cyclohexane of100 lg ml�1 was obtained from Dr. Ehrenstorfer GmbH(Augsburg, Germany). Individual analytical-reagent gradePCB congeners, 28, 52, 101, 105, 118, 128, 138, 149, 153,156, 170 and 180, at purity higher than 99%, were suppliedby Promochem GmbH (Wesel, Germany). A stock stan-dard solution mixture of the 12 PCB congeners at300 ng ml�1 was prepared by weight in isooctane fromthe individual standard solutions. Five calibration stan-dard solutions of SCCPs (between 1 and 80 lg ml�1) andPCBs (from 0.5 to 200 ng g�1) were prepared by dilutionof the primary standard solutions in isooctane for

1554 P. Castells et al. / Chemosphere 70 (2008) 1552–1562

quantification purposes. PCB-30 (Dr. Ehrenstorfer GmbH)was used as internal standard for quantification of PCBcongeners while 13C6-hexachlorobenzene (Dr. Eherenstor-fer GmbH) was used for quantification of PCNs andSCCPs.

Supelclean ENVI-Carb SPE non-porous graphitisedcarbon black cartridges (250 mg, 3 ml, 120/140 mesh and100 m2 g�1) were obtained from Supelco (Bellefonte, PA,USA). Cyclohexane, n-hexane, dichloromethane, isooctaneand toluene for residue analysis (Merck) were used as sol-vents. Florisil (0.150–0.250 mm) for residue analysis, finecopper powder (particle size <63 lm) and anhydroussodium sulphate, all of analytical grade, were purchasedfrom Merck (Darmstadt, Germany).

2.2. Sampling

Nine coastal marine sediment samples were collectedduring year 2003 at a depth of 20, 30 or 50 m near themouth of Besos River (Barcelona, NE Spain). In addition,four marine sediment samples were collected near a sub-marine emissary located at 2 km from the mouth of BesosRiver, and coming from the waste water treatment plant(WWTP) of the Besos River. All samples were collectedusing a Van Veen grab sampler (sampling area of0.1 m2). Sediments were air-dried, grounded, sieved usinga 125-lm mesh, homogenized and stored in sealed contain-ers at +4 �C under analysis. The organic carbon of thesesamples were determined and ranged between 1.5% and4% for coastal marine sediments and from 4% to 7% forsubmarine emissary sediments.

2.3. Extraction, clean-up and fractionation

Sediment samples (10 g) were mixed with 20 g of anhy-drous sodium sulphate and 20 g of activated copper pow-der for sulphur removal and were Soxhlet extracted for16 h using 300 ml of n-hexane:dichloromethane (DCM)(1:1, v/v). The extracts were concentrated to 5 ml by rotaryevaporation and then to ca. 1 ml using a stream of nitro-gen. After that, each extract was loaded onto a glass col-umn containing 20 g of Florisil (activated at 650 �C for12 h). Three fractions were obtained, using (a) 60 ml of n-hexane, where PCBs were eluted (Fraction 1), (b) 150 mlof a n-hexane:dichloromethane mixture (3:1, v/v) whichcontained tri- to octachloronaphthalenes (Fraction 2),and (c) 200 ml of n-hexane:dichloromethane (1:1, v/v)where SCCPs were obtained (Fraction 3). Fraction 1 and3 were rotary concentrated and the final volume wasadjusted to 100 ll after addition, respectively, of PCB-30and 13C6-hexachlorobenzene as internal standards. Thefinal extracts were analysed by GC-ECD and GC–ECNI-MS, respectively. Fraction 2 was concentrated up to100 ll and further fractionated using an ENVI-Carbgraphitised carbon black cartridge (250 mg, 3 ml) in orderto avoid potential chlorinated interferences such aschlordane and related compounds (Malavia et al., 2004;

Sobrado et al., 2004; Kleinhenz et al., 2006; Karla andRuoffb, 2007). Before use, the cartridges were washedand conditioned using 20 ml of n-hexane, 20 ml of tolueneand finally 20 ml of n-hexane. The sample extract wasadded to the cartridge and the first fraction obtained with15 ml of n-hexane was discarded. A second fraction con-taining the tri- to octachloronaphthalenes was collectedusing 25 ml of n-hexane:toluene (1:1, v/v). This fractionwas then concentrated up to 100 ll and analysed byGC–IT-MS/MS after adding to the extract an adequateamount of 13C6-hexachlorobenzene as internal standard.

2.4. Analysis, identification and quantification

Both PCNs and SCCPs were determined using a TraceGC 2000 gas chromatograph (ThermoFinnigan, Milan,Italy) coupled with a GCQ/Polaris ion-trap mass spectrome-ter (ThermoFinnigan, Austin, TX, USA). A DB-5 (5% phe-nyl-, 95% methylpolysiloxane), 60 m · 0.25 mm i.d., fused-silica capillary column (J&W Scientific, Folsom, USA) of0.25 lm film thickness was used for separation of PCN cong-eners, whereas for SCCPs, a DB-5ms column of 30 m ·0.25 mm i.d., fused-silica capillary column (J&W Scientific,Folsom, USA) of 0.25 lm film thickness was used. The car-rier gas was helium at a constant flow-rate of 1 ml min�1 heldby electronic pressure control. An injector temperature of250 �C and splitless injection mode (1 min) were used. Forsamples and standards, the injection volume was 1 ll. ForPCNs the oven temperature program was 90 �C (held for1 min), raised to 160 �C at 10 �C min�1, and then to 300 �Cat 2 �C min�1 (held for 10 min), while for SCCPs, the pro-gram was 90 �C (held for 1 min) to 180 �C at 15 �C min�1

and to 300 �C at 8 �C min�1 (held for 10 min).MS operating conditions for PCN determination were:

ion source and transfer line temperatures 200 �C and280 �C, respectively, electron energy 70 eV and emissioncurrent 250 lA. The instrument was tuned in EI positivemode using perfluorotributylamine (FC-43). Parameterssuch as automatic gain control (AGC) and multiplier volt-age (1450 V, 105 gain) were set by automatic tune. For full-scan mode a mass range of 45–650 m/z was used at a scanrate of 0.76 s per scan (4 lscans per scan). For quantifica-tion of tri- to octa-CNs the ion-trap mass spectrometerwas operated in the MS/MS mode. The optimum MS/MS operating parameters were the following: CID excita-tion amplitude, 1.30 V; maximum excitation energy, qz,0.45; isolation window of precursor ion, 1 m/z; isolationtime, 8 ms; excitation time, 15 ms. The acquisition methodwas programmed in different segments for each PCNhomologue group and product ions were monitored at ascan rate of 0.65 s per scan (7 lscans per scan).

For the analysis of SCCPs, the instrument was operatedin the ECNI mode. Parameters such as electron energy,emission current, and multiplier voltage were the same asfor the case of PCNs. Ion source and transfer line temper-atures were 250 �C and 275 �C, respectively. Methane wasused as moderating gas at a pressure of 1.2 · 10�4 mTorr

P. Castells et al. / Chemosphere 70 (2008) 1552–1562 1555

(reading on the ion gauge), measured by means of an iongauge in the mass analyser region of the vacuum manifold.The MS acquisition method was time programmed in twosegments. In the first segment, the internal standard 13C6-hexachlorobenzene was detected by monitoring the 286–296 m/z region at 0.64 s per scan (10 lscan per scan),whereas SCCPs were monitored in the second segment byscanning the range m/z 70–75 ([HCl2]� and [Cl2]�. clusterions) at 0.63 s per scan (10 lscan per scan). SCCPs werequantified as the sum of total area below the elution profileof SCCPs obtained in the second monitoring segment.Xcalibur version 1.2 software was used for instrumentcontrol and data acquisition. A SCCP standard mixture(C10–C13, 63% Cl) of similar composition than that of sed-iments was used for quantification (Korytar et al., 2005).

Identification of PCN congeners was performed using astandard solution of Halowax 1014 according to the reten-tion order reported in the literature by Kannan et al.(2000). In addition, the isotopic ratio of the two monitoredproduct ions obtained in MS/MS mode was used for iden-tification. Differences in the isotopic ratio between the the-oretical and the observed values lower than ±15% wereused as confirmation criterium (Table 1). Quantificationof PCNs was carried out using the internal standardmethod. Calibration standard solutions were prepared bydilution of the stock standard solution (PCN-MXA) con-taining the eight PCN congeners stated in Section 2.1. Cal-ibration graphs obtained for each congener were used forthe quantification, assuming that the responses of congen-ers for each chlorination degree were the same as of thecorresponding congener used for calibration (Eljarratet al., 1999; Kannan et al., 2000).

PCB determination was performed using a Trace GC2000 gas chromatograph (ThermoFinnigan, Milan, Italy),equipped with a 63Ni electron-capture detector (ECD).Chromatographic separation of PCB congeners was per-formed on the same DB-5ms column used for SCCPs. Inaddition, confirmation of the twelve PCB congeners wascarried out using a DB-17 (50% phenyl-, 50% meth-ylpolysiloxane), 30 m · 0.25 mm i.d., fused-silica capillarycolumn (J&W Scientific) of 0.25 lm film thickness. Heliumwas used as carrier gas at a constant flow-rate of1 ml min�1 held by electronic pressure control and N2 as

Table 1Precursor ions and product ions selected for each PCN homologue group

Homologue Precursor ion (m/z) Produ

Tri-CNs 232 [M+2]+� 162/16Tetra-CNs 266 [M+2]+� 196/19Penta-CNs 300 [M+2]+� 230/22Hexa-CNs 334 [M+2]+� 264/26Hepta-CNs 368 [M+2]+� 298/29Octa-CN 404 [M+4]+� 334/3313C6-HCB (I.S.) 290 [M+2]+� 255/25

Other conditions: qz value, 0.45; isolation window, 1.0; isolation time, 8 ms; excemission current, 250 lA; lscans/scan, 4. CN: chlorinated naphthalene; HCB:

a Theoretical isotopic ratios are given in brackets.

ECD make-up gas (40 ml min�1). Injector and ECD tem-perature were set at 250 �C and 330 �C, respectively, andthe splitless injection mode (1 min) was used. The oven pro-gramme for both DB-5ms and DB-17 capillary columnswas: 90 �C (held for 1 min) to 180 �C at 15 �C min�1 andto 300 �C at 2.5 �C min�1.

2.5. Quality control criteria

A daily isomer-specific GC separation test, sensitivitytest and calibration test were carried out. Proceduralblanks (both instrumental and method) were routinely per-formed during the analysis and quality control sedimentsamples were periodically analyzed in order to ensurethat the analytical method was maintained under control.A sediment sample with non-detectable amounts of thePCNs and SCCPs spiked, respectively, at 1 ng g�1 dw and0.40 lg g�1 dw was used as quality control sample, whilefor PCBs the certified reference material CRM-536 wasused.

3. Results and discussion

3.1. GC/ITMS conditions

For PCN analysis, several MS/MS parameters of theion-trap mass analyser were adjusted in order to enhancesensitivity and selectivity. A standard solution (PCN-MXA) containing one individual congener representativeof each studied homologue group (tri- to octa-CNs) wasused for collision induced dissociation (CID) optimisation.For all congeners the spectrum was characterized by a basepeak corresponding to the molecular ion along with thefragment ions [M�2Cl]+� and [M�Cl]+ with lower abun-dances, in agreement with the literature data (Wanget al., 2005; Yusa et al., 2006). As an example, Fig. 1 showsthe EI full-scan spectrum obtained for 1,2,3,5,7-pentaCN.The most abundant ion of the molecular cluster, the[M+2]+� for tri- to hepta-CNs and the [M+4]+� for octa-CN, was selected as precursor ion. Product ions corre-sponding to the loss of two chlorine atoms from each pre-cursor ion were monitored for quantification andidentification purposes (Table 1), since they showed the

ct ions (m/z) Isotopic ratioa

0 [M+2-35Cl2]+�/[M+2-35Cl37Cl]+� 0.446 (0.5)4 [M+2-35Cl2]+�/[M+2-35Cl37Cl]+� 1.076 (1.0)8 [M+2-35Cl2]+�/[M+2-35Cl37Cl]+� 1.595 (1.5)2 [M+2-35Cl2]+�/[M+2-35Cl37Cl]+� 2.041 (2.0)6 [M+2-35Cl2]+�/[M+2-35Cl37Cl]+� 2.545 (2.5)2 [M+4-35Cl2]+�/[M+4-35Cl37Cl]+� 1.309 (1.25)3 [M+2-35Cl]+/[M+2-37Cl]+ 5.391 (5.0)

itation time, 15 ms; ion source temperature, 200 �C; electron energy, 70 eV;hexachlorobenzene.

Rel

ativ

e A

bund

ance

(%

)

120 140 160 180 200 220 240 260 28 300 320 340 360 380 400 420

m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100[M]+ ••••

[M-Cl]+ ••••

[M-2Cl]+ ••••

120 140 160 180 200 220 240 280 300 320 340 360 380 400 4200

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

[M]+ ••••

[M-Cl]+ ••••

[M-2Cl]+ ••••

Fig. 1. EI full-scan spectrum obtained for 1,2,3,5,7-pentaCN.

1556 P. Castells et al. / Chemosphere 70 (2008) 1552–1562

highest relative abundances in the MS/MS spectra. Theeffect of CID excitation amplitude on the product ion yieldwas studied for each PCN homologue group and for theinternal standard (13C6-hexachlorobenzene) using 0.2 Vincrements. Fig. 2 shows the excitation amplitude break-down curves obtained for the eight PCN congeners studied.Maximum abundances of the selected product ions wereobtained using a CID value of 1.30 V. For the internalstandard 13C6-hexachlorobenzene (13C6-HCB), the twomost intense [M�Cl]+ product ions were chosen for CIDoptimisation, and an optimum CID value of 1.30 V wasused.

Additional experiments were performed in order to setthe proper value for the excitation energy (qz parameter).This parameter was studied at three qz levels: 0.225, 0.300and 0.450 and showed a significant effect on the abun-

0

5000

100000

150000

200000

250000

300000

0.70 0.90 1.10 1.30 1.50 1

CID excitation ampl

Pea

k ar

ea

Fig. 2. CID excitation amplitude breakdown curves

dances of product ions. The highest abundances wereobtained using a qz value of 0.450. The effect of excitationtime, from 10 to 30 ms in 5 ms steps, was also studied. Anincrease of the excitation time produced a moderateenhancement on the fragmentation yield, but the timerequired for a MS/MS scan also increased producing adecrease in the response. Therefore, an excitation time of15 ms was chosen as a compromise. Finally, a further rele-vant MS/MS parameter such as precursor mass isolationwidth was also adjusted in order to further enhance sensi-tivity and selectivity for the detection of PCN congeners.The effect of the mass isolation window on the selective iso-lation of the precursor ion was investigated from 1 to 3 m/zusing sediment samples. This parameter is probably themost important to consider when dealing with real matriceswhich contain potentially interfering compounds, and a

.70 1.90 2.10 2.30

itude (V)

Mono-CNs

Di-CNs

Tri-CNs

Tetra-CNs

Penta-CNs

Hexa-CNs

Hepta-CNs

Octa-CNs

obtained for the eight PCN congeners studied.

Table 2Mean recoveries, run-to-run precision and LODs obtained for individualPCN congeners, PCB congeners and SCCPs in sediments

Meanrecoverya

(%)

Run-to-runb

(% RSD)

LODs(ng g�1)

1,2,3-TriCN (PCN-13) 76 7 0.0031,2,3,5-TetraCN (PCN-28) 83 5 0.0021,2,3,5,7-PentaCN (PCN-52) 91 7 0.0011,2,3,4,6,7-HexaCN (PCN-66) 96 5 0.0011,2,3,4,5,6,7-HeptaCN (PCN-73) 98 8 0.001Octa-CN (PCN-75) 94 6 0.002PCB-28 95 6 0.010PCB-52 93 8 0.014PCB-101 95 6 0.010PCB-105 93 7 0.008PCB-118 90 6 0.008PCB-128 91 6 0.012PCB-138 94 7 0.006PCB-149 93 6 0.008PCB-153 97 6 0.014PCB-156 97 7 0.014PCB-170 94 7 0.010PCB-180 95 6 0.010SCCPs 95 3 1.8

a n = 3.b n = 5.

P. Castells et al. / Chemosphere 70 (2008) 1552–1562 1557

mass isolation window of 1 m/z was found to be the bestchoice in order to keep a compromise between sensitivityand selectivity.

For the analysis of SCCPs, the instrument was operatedin the ECNI mode. Optimum ECNI-MS conditions werethose established in a previous work (Castells et al.,2004a,b) and are given in Section 2.4.

Table 3PCN (ng g�1 dw), PCB (ng g�1 dw) and SCCP (lg g�1 dw) concentrations in

Compound Coastal marine sediments

C1 C2 C3 C4 C5 C6

RTri-CNs 0.51 0.29 0.01 0.89 0.74 11.17RTetra-CNs 1.07 0.36 0.10 0.41 1.31 1.32RPenta-CNs 0.73 0.10 0.05 0.11 0.35 0.41RHexa-CNs 0.25 0.02 0.01 0.04 0.08 0.10RHepta-CNs n.d. n.d. n.d. n.d. 0.04 0.04Octa-CN n.d. n.d. n.d. n.d. 0.09 n.d.Total PCNs 2.56 0.77 0.17 1.44 2.62 2.98

PCB 28 1.38 n.d. n.d. 5.57 4.38 1.63PCB 52 1.98 n.d. n.d. n.d. 4.58 n.d.PCB 101 1.64 1.29 1.56 2.64 4.01 4.00PCB 149 n.d. n.d. n.d. n.d. 4.75 1.49PCB 118 n.d. n.d. 0.80 n.d. 4.07 n.d.PCB 153 n.d. n.d. 5.78 1.78 5.77 n.d.PCB 105 0.73 n.d. 3.37 n.d. 5.63 2.50PCB 138 n.d. n.d. n.d. n.d. 2.96 n.d.PCB 128 n.d. n.d. 0.25 1.32 1.32 n.d.PCB 156 1.42 1.04 n.d. n.d. 0.39 n.d.PCB 180 n.d. n.d. n.d. 0.81 4.41 1.14PCB 170 n.d. n.d. 6.06 n.d. 1.73 n.d.Total PCBs 7.15 2.33 17.83 12.12 44.00 10.76

Total SCCPs 0.67 0.46 0.40 1.17 0.71 0.21

n.d.: not detected.

Limits of detection and run-to-run precision were deter-mined for PCNs, SCCPs and PCBs (Table 2). Limits ofdetection (LODs) were calculated as the amount of analytethat produced a signal-to-noise ratio (S/N) of 3:1. LODdetermination was performed by analysing sediment sam-ple extracts without detectable quantities of PCNs, SCCPsand PCBs, which were spiked with appropriate amountsof analytes at low concentration levels. Limits of detectionfor PCNs using GC–MS/MS expressed on a dry weight(dw) basis ranged from 0.001 to 0.003 ng g�1. The LODobtained for SCCPs using GC–ECNI-MS was 1.8ng g�1 dw, whereas for PCB congeners, LODs ranged from0.006 to 0.014 ng g�1 dw using GC-ECD.

Run-to-run precision was also established for PCNs,SCCPs and PCBs in sediment samples. For this purpose,five replicates of a blank sediment sample spiked withPCN, SCCP and PCB standard solutions at a concentra-tion level of 0.1 ng g�1, 200 ng g�1 and 2 ng g�1, respec-tively, were analysed within one day. A relative standarddeviation (RSD) of 3% was obtained for SCCPs, whereasfor PCNs and PCBs, values ranging from 5% to 8% andfrom 6% to 8%, were found (Table 2).

Finally, recoveries for the overall analytical procedurewere determined for tri- to octa-CNs using blank sedimentsspiked at three concentration levels (0.2, 0.3 and0.4 ng g�1 dw) of each of the corresponding individualtri- to octa-CN individual congeners present in the PCN-MXA standard mixture. Recoveries obtained for the indi-vidual congeners were assumed to be the same for each cor-responding homologue group with the same chlorinationlevel. To determine the recovery of PCBs and SCCPs, ablank sediment was spiked at three different concentration

marine sediments

Submarine emissary sediments

C7 C8 C9 S1 S2 S3 S4

0.96 0.33 0.27 n.d. n.d. 0.04 0.201.36 0.66 0.51 0.22 0.05 0.11 0.240.56 0.38 0.20 310.7 0.15 0.11 0.170.25 0.27 0.07 0.06 n.d. 0.03 0.020.09 0.06 n.d. 0.77 0.94 0.43 0.430.06 0.02 n.d. 5.21 3.65 1.28 2.273.27 1.72 1.04 6.56 4.80 2.02 3.13

1.56 n.d. n.d. 2.41 2.98 2.24 2.105.97 5.62 1.67 2.19 2.36 1.49 1.300.95 2.18 0.70 2.72 0.98 1.35 1.23n.d. n.d. n.d. 6.13 2.08 3.57 3.334.84 5.81 2.61 3.29 10.36 1.92 1.60n.d. n.d. n.d. 7.70 3.32 5.48 4.73n.d. 3.83 n.d. 0.83 1.51 0.44 n.d.2.70 n.d. n.d. 3.97 2.93 4.50 6.776.43 n.d. n.d. 0.58 n.d. 0.22 n.d.1.06 4.63 n.d. 0.42 n.d. 0.16 0.07n.d. n.d. 2.12 4.94 3.52 3.58 3.37n.d. n.d. n.d. 2.56 1.60 1.91 1.7123.51 22.05 7.10 37.74 22.64 26.86 26.21

0.80 0.29 0.26 2.09 1.81 1.42 1.25

1558 P. Castells et al. / Chemosphere 70 (2008) 1552–1562

levels (200, 300 and 400 ng g�1 dw for SCCPs, and 2, 3 and4 ng g�1 dw for individual PCB congeners). The sampleswere subjected to the whole analytical procedure andrecoveries were calculated from the slope of the curveobtained by plotting the ng recovered per g of sediment ver-

sus the ng spiked per g of sediments. Mean recoveriesobtained for the individual PCN congeners ranged between76% and 98% for tri- to octa-CNs, whereas recoveries rang-ing from 87% to 97% were obtained for PCB congeners,and a recovery value of 95% was obtained for SCCPs.

3.2. Analysis of sediment samples

PCNs, PCBs and SCCPs were determined in marine sed-iments collected in Barcelona (NE Spain) and the results aregiven in Table 3. As an example, the characteristic MS/MS

24 25 26 27 28 29

Time (min)

0

50

100

Rel

ativ

e A

bund

ance

(%

)

19

24/14

15

16

17/25

23

18

Tri-CNs

39 40 41 42 43 44 45 46 47

Time (min)

52/60

58

61

5051

54

57

6253/55

59

4956

Penta-CNs

0

50

100

Rel

ativ

e A

bund

ance

(%

)

55 56 57 58 59 60 61 62 63

Time (min)

73Hepta-CNs

0

50

100

Rel

ativ

e A

bund

ance

(%

)

Fig. 3. MS/MS chromatogram for tri- to octachloronaphthalene homolo

chromatogram for tri- to octachloronaphthalene homo-logues detected in a sample of coastal marine sediments(sample C3) is given in Fig. 3. Total concentrations of tri-through octa-CNs expressed on a dry weight (dw) basis ran-ged from 0.17 to 6.56 ng g�1 dw (Table 3). These results areconsistent with data published in the literature for marinesediments collected in the Tokyo Bay (Japan, Yamashitaet al., 2000a,b) (1.8–4.4 ng g�1 dw), in Gothenburg harbour(Sweden, Jaernberg et al., 1993) (1.0–1.3 ng g�1 dw), inVenice and Orbetello lagoons (Italy, Eljarrat et al., 1999)(0.03–1.5 ng g�1 dw) in Quingdao coastal sea (China, Panet al., 2007) (0.1–5.5 ng g�1 dw) and in Gulf of Bothnia(northern Baltic Sea, Sweden, Lundgren et al., 2003)(0.27–2.8 ng g�1 dw). In these samples, the percentages foreach PCN homologue group showed a higher proportionof tri- and tetra-CNs (Fig. 4a) than that observed for

29 30 31 32 33 34 35 36 37 38

Time (min)

42

33/34/37

47

36/45

28/43

29

30/27/39

32/4835

38/40

46

41

Tetra-CNs

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50

100

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ance

(%

)

48 49 50 51 52 53 54

66/67

64/68

69

71/72

63

65

Hexa-CNs

Time (min)

0

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100

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ativ

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bund

ance

(%

)

75

Octa-CN

0

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100

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ance

(%

)

66 68 70 72

Time (min)69 716765

gues detected in a sample of coastal marine sediments (sample C3).

0

20

40

60

80

100

Tri-CNs Tetra-CNs Penta-CNs Hexa-CNs Hepta-CNs Octa-CN

Tri-CNs Tetra-CNs Penta-CNs Hexa-CNs Hepta-CNs Octa-CN

% C

om

po

siti

on

0

20

40

60

80

100

% C

om

po

sitio

n

a

b

Fig. 4. Tri-CN to octa-CN composition (%) for (a) a coastal sedimentsamples and (b) a sediment samples collected near the submarine emissary.

P. Castells et al. / Chemosphere 70 (2008) 1552–1562 1559

Halowax 1014, in agreement with data published in the lit-erature (Jarnberg et al., 1997; Eljarrat et al., 1999; Gevaoet al., 2000; Yamashita et al., 2000a,b; Meijer et al., 2001;Krauss and Wilcke, 2003; Lundgren et al., 2003). In addi-tion, the relative distribution pattern of the individualPCN congeners within each PCN homologue group wassimilar to that reported by other authors (Gevao et al.,2000; Meijer et al., 2001; Krauss and Wilcke, 2003). In con-trast, sediments collected near the submarine emissary (S1–S4) coming from a wastewater treatment plant (WWTP)showed a notable enrichment on hepta-CNs and octachlo-ronaphthalene. In particular, the proportion of hepta-CNs was between 12% and 21% of the total PCNs, beingeven higher for octachloronaphthalene, from 64% to 79%.This distribution of PCN homologues (Fig. 4b) closelyresembled that observed in Halowax 1051 (Noma et al.,2004), so this technical mixture could be the source of con-tamination. Nevertheless, some authors suggest that thiskind of PCN distribution could be due to a contaminationof sediments with highly chlorinated technical PCB formu-lations (Martı and Ventura, 1997; Kannan et al., 2000;Yamashita et al., 2000a,b; Helm and Bidleman, 2003;Falandysz and Puzyn, 2004; Noma et al., 2004; Taniyasuet al., 2005), which can contain PCNs as impurities from1.8 to 870 lg g�1, and proportions of hepta- and octa-CNquite similar to Halowax 1051. However, in our case thishypothesis is not applicable since PCB concentration levelsin the sediment samples, between 2.3 and 44 ng g�1 dw,were only ca. 10-fold higher than those of PCNs.

Regarding SCCPs, total CP concentrations expressed ona dry weight basis varied from 0.21 to 2.09 lg g�1 dryweight (Table 3). As an example, the GC–ECNI-MS chro-matograms obtained for sediment sample C3 and a stan-dard of SCCP mixture (C10–C13, 63% Cl) are given inFig. 5. These results are relatively high, ca. one order ofmagnitude higher than the concentrations generally foundin marine sediments collected in different parts of theworld such as Canada (Tomy et al., 1999a) (0.005–0.257ng g�1 dw), Czech Republic (Stejnarova et al., 2005)(0.005–0.181 ng g�1 dw), Baltic Sea (Huittig et al., 2004;Huittig and Oehme, 2005) (0.005–0.377 ng g�1 dw), andJapan (Iino et al., 2005). However, the levels obtained inour work are similar to the low range values reported fromsediments and soils collected in industrial or semi-indus-trial areas from Germany (Kemmlein et al., 2002) (2.14–189 lg g�1 dw), England and Wales (Nicholls et al.,2001)) (0.2–65.1 lg g�1 dw), and the USA (Murray et al.,1999) (0.76–170 lg g�1 dw). In fact, levels of SCCPs foundin the marine sediment samples analysed in this study(0.21–2.09 lg g�1 dw) are similar to those obtained in aprevious work (0.27–3.26 lg g�1 dw) (Castells et al.,2004a,b), in which SCCPs were analysed in river sedimentsamples collected in the mouth of the Besos River (Barce-lona, NE Spain). Since this river flows into the coastal mar-ine area examined in the present study, the results show arelatively uniform contamination by short-chain CPs inthis area of Barcelona and a diffuse input of SCCPs tothe marine environment.

The sum of 12 PCB congeners found in this study for thesample locations in the coastal marine area varied between2.33 and 23.51 ng g�1 dw (Table 3), except for one sitein which the PCB concentration was higher (44.00ng g�1 dw). Apart from this sample, levels observed arevery similar to those obtained in a previous study for sed-iments collected at the Besos River (Parera et al., 2002)(2.47–24.21 ng g�1 dw), confirming diffuse but uniforminputs of PCBs in the whole area as for SCCPs. How-ever, the results obtained for sites located near thesubmarine emissary were generally slightly higher (22.64–37.74 ng g�1 dw). The same trend was observed for PCNs,with levels ranging from 0.17 to 3.3 ng g�1 dw in thecoastal area versus 2.0–6.6 ng g�1 dw near the submarineemissary, and also for SCCPs (0.21–1.17 lg g�1 dw versus

1.25–2.09 lg g�1 dw). Sediments on this area have beenfor years under permanent discharges of primary sludgeand effluents coming from a wastewater treatment plant,which spread out over a certain perimeter close to the dis-charge area. Therefore, the high levels of PCNs, PCBs andSCCPs found in the samples collected in the submarineemissary area could be attributed to continuous inputs ofeffluent water with contaminated particulate matter comingfrom the emissary. These results are in agreement with datareported for coastal areas under the influence of WWTPeffluents and sewage sludges along the Catalonia coastalarea for polybrominated diphenyl ethers (PBDEs), poly-chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/

I.S.

I.S.

10 12 14 16 18 20 22 24 26 28 30 328 34

a

b

36

Rel

ativ

e A

bun

dan

ce(

%)

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ativ

e A

bun

dan

ce(

%)

Time (min)

40

20

60

80

100

0

40

20

60

80

100

0

Fig. 5. GC–ECNI-MS chromatograms of (a) SCCPs detected in a sample of coastal marine sediments (sample C3) and (b) a 5 lg ml�1 standard solutionof the SCCP C10–C13, 63% Cl. For each chromatogram, detection of the internal standard (I.S. 13C6-hexachlorobenzene, m/z 286–296) and the SCCP(m/z 70–75) is shown.

1560 P. Castells et al. / Chemosphere 70 (2008) 1552–1562

Fs) and PCBs (Borrull et al., 2001; Eljarrat et al., 2001,2005), and also in other Mediterranean coastal sites likeMarseille (France) for PCBs and DDT (Wafo et al., 2006).

4. Conclusions

PCNs, SCCPs and PCBs were detected in all the marinesediments, showing their ubiquity in the coastal area ofBarcelona. Relatively high contamination levels of the tar-get compounds were found in the samples collected andcan be attributed to diffuse but uniform inputs of these pol-lutants to the marine environment. Higher contaminationlevels for the three groups of compounds have been foundin samples collected near the submarine emissary. Regard-ing the specific-congener profiles, samples collected near tothe submarine emissary showed a different PCN congenerdistribution than that observed for the coastal sedimentsamples. The PCN profile found in the coastal sedimentsamples resembled to the PCN technical mixture Halowax1014, whereas the samples collected near the submarineemissary showed higher proportions of hepta- and octa-CN. This different distribution could be attributed toinputs of sewage sludge contaminated with Halowax1051. Further research work should be performed in order

to establish a more detailed assessment of the target com-pound levels in this area.

Acknowledgement

The authors acknowledge the financial support providedby the Ministerio de Ciencia y Tecnologıa (CTM2006-00753/TECNO).

References

Abad, E., Caixach, J., Rivera, J., 1999. Dioxin like compounds frommunicipal waste incinerator emissions: assessment of the presence ofpolychlorinated naphthalenes. Chemosphere 38, 109–120.

Borrull, F., Marced, R.M., Barcelo, D., 2001. Evaluation of dioxincontamination in sewage sludge discharges on coastal sediments fromCatalonia, Spain. Water Res. 35, 2799–2803.

Brack, W., Kind, T., Schrader, S., Moder, M., Schuurmann, G., 2003.Polychlorinated naphthalenes in sediments from the industrial regionof Bitterfeld. Environ. Pollut. 121, 81–85.

Braune, B.M., Outridge, P.M., Fisk, A.T., Muir, D.C., Helm, P.A.,Hobbs, K., Hoekstra, P.F., Kuzyk, Z.A., Kwan, M., Letcher, R.J.,Lockhart, W.L., Norstrom, R.J., Stern, G.A., Stirling, I., 2005.Persistent organic pollutants and mercury in marine biota of theCanadian Arctic: an overview of spatial and temporal trends. Sci.Total Environ. 351–352, 4–56.

Carrizo, D., Grimalt, J.O., 2006. Rapid and simplified method for theanalysis of polychloronaphthalene congener distributions in

P. Castells et al. / Chemosphere 70 (2008) 1552–1562 1561

environmental and human samples by gas chromatography coupled tonegative ion chemical ionization mass spectrometry. J. Chromatogra-phy A. 1118, 271–277.

Castells, P., Santos, F.J., Galceran, M.T., 2003. Solid-phase microextrac-tion for the analysis of short-chain chlorinated paraffins in watersamples. J. Chromatogr. A 984, 1–8.

Castells, P., Santos, F.J., Galceran, M.T., 2004a. Evaluation of threeionisation modes for the analysis of chlorinated paraffins by gaschromatography/ion-trap mass spectrometry. Rapid Commun. MassSpectrom. 18, 529–536.

Castells, P., Santos, F.J., Galceran, M.T., 2004b. Solid-phase extractionversus solid-phase microextraction for the determination of chlori-nated paraffins in water using gas chromatography–negative chemicalionisation mass spectrometry. J. Chromatogr. A 1025, 157–162.

CEPA, 1993. Government of Canada. Environment Canada. Health andWelfare. Canadian Environmental Protection Act, Priority SubstancesList Assessment Report. Chlorinated Paraffins.

Coelhan, M., 1999. Determination of Short-Chain PolychlorinatedParaffins in Fish Samples by Short-Column GC/ECNI-MS. Anal.Chem. 71, 4498–4505.

Egeback, A.L., Wideqvist, U., Jarnberg, U., Asplund, L., 2004. Polychlo-rinated naphthalenes in Swedish background air. Environ. Sci.Technol. 38, 4913–4920.

Eljarrat, E., Caixach, J., Jimenez, B., Gonzalez, M.J., Rivera, J., 1999.Polychlorinated naphthalenes in sediments from the Venice andOrbetello Lagoons, Italy. Chemosphere 38, 1901–1912.

Eljarrat, E., Caixach, J., Rivera, J., 2001. Evaluation of dioxin conta-mination in sewage sludge discharges coastal sediments fromCatalonia, Spain. Wat. Res. 35, 2799–2803.

Eljarrat, E., De La Cal, A., Larrazabal, D., Fabrellas, B., Rodrıguez, A.,Fernandez, A., Borrull, F., Marce, R.M., Barcelo, D., 2005. Occur-rence of polybrominated diphenylethers, polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in coastal sediments from Spain.Environ. Pollut. 136, 493–501.

Engwall, M., Brundstrom, B., Jakobsson, E., 1994. Ethoxyresorufin O-deethylase (EROD) and aryl hydrocarbon hydroxylase (AHH)-induc-ing potency and lethality of chlorinated naphthalenes in chicken(Gallus domesticus) and eider duck (Somateria mollissima) embryos.Arch. Toxicol. 68, 37–42.

EPA, 1991. U.S. Environmental Protection Agency. Office of ToxicSubstances. Chlorinated Paraffins. Environmental and Risk Assess-ment, RM1 Decision Package, Washington DC.

Falandysz, J., 1998. Polychlorinated naphthalenes: an environmentalupdate. Environ. Pollut. 101, 77–90.

Falandysz, J., 2003. Chloronaphthalenes as food-chain contaminants: areview. Food Addit. Contam. 20, 995–1014.

Falandysz, J., Puzyn, T., 2004. Computational prediction of 7-ethoxyres-orufin-O-diethylase (EROD) and luciferase (luc) inducing potency for75 congeners of chloronaphthalene. J. Environ. Sci. Health A 39,1505–1523.

Gevao, B., Harner, T., Jones, K.C., 2000. Sedimentary record ofpolychlorinated naphthalene concentrations and deposition fluxes ina Dated Lake core. Environ. Sci. Technol. 34, 33–38.

Harner, T., Shoeib, M., Gouin, T., Blanchard, P., 2006. Polychlorinatednaphthalenes in Great Lakes air: assessing spatial trends combustioninputs using PUF disk passive air samplers. Environ. Sci. Technol. 40,5333–5339.

Hayward, D.G., 1998. Identification of bioaccumulating polychlorinatednaphthalenes and their toxicological significance. Environ. Res. 76,1–18.

Helm, P.A., Bidleman, T.F., 2003. Current combustion-related sourcescontribute to polychlorinated naphthalene and dioxin-like polychlori-nated biphenyl levels and profiles in air in Toronto, Canada. Environ.Sci. Technol. 37, 1075–1082.

Huittig, J., Oehme, M., 2005. Congener group patterns of short andmedium chain chloroparaffins in marine sediments. OrganohalogenCompds. 67, 2041–2043.

Huttig, J., Oehme, M., 2006. Congener group patterns of chloroparaffinsin marine sediments obtained by chloride attachment chemicalionization and electron capture negative ionization. Chemosphere 64,1573–1581.

Huittig, J., Zencak, Z., Oehme, M., 2004. Levels of chlorinated paraffins inNorth and Baltic Sea sediments. Organohalogen Compds. 66, 1321–1326.

Iino, F., Takasuga, T., Senthilkumar, K., Nakamura, N., Nakanishi, J.,2005. Risk assessment of short-chain chlorinated paraffins in Japanbased on the first market basket study and species sensitivitydistributions. Environ. Sci. Technol. 39, 859–866.

International Agency for Research on Cancer (IARC). Monograph, 1990.Environmental Protection Agency. Office of Toxic Substances. Chlo-rinated Paraffins. Environmental and Risk Assessment, RM1 DecisionPackage, Washington DC, 1991.

Jaernberg, U., Asplund, L., de Wit, C., Grafstrom, C., Haglund, P.,Jansson, B., Lexen, K., Strandell, M., Olsson, M., Jonsson, B., 1993.Polychlorinated biphenyls and polychlorinated naphthalenes in Swed-ish sediment and biota: levels, patterns, and time trends. Environ. Sci.Technol. 27, 1364–1374.

Jarnberg, U., Asplund, L., de Wit, C., Egeback, A.I., Widequist, U.,Jakobsson, E., 1997. Distribution of polychlorinated naphthalenecongeners in environmental and source-related samples. Arch. Envi-ron. Contam. Toxicol. 32, 232–245.

Kannan, K., Imagawa, T., Blankenship, A.L., Giesy, J.P., 1998. Isomer-specific analysis and toxic evaluation of polychlorinated naphthalenesin soil, sediment, and biota collected near the site of a former chlor-alkali plant. Environ. Sci. Technol. 32, 2507–2514.

Kannan, K., Yamashita, N., Imagawa, T., Decoen, W., Khim, J.S., Day,R.M., Summer, C.L., Giesy, J.P., 2000. Polychlorinated naphthalenesand polychlorinated biphenyls in fishes from Michigan waters includ-ing the Great Lakes. Environ. Sci. Technol. 34, 566–572.

Karla, H., Ruoffb, U., 2007. Dioxins, dioxin-like PCBs and chloroorganiccontaminants in herring, Clupea harengus, from different fishinggrounds of the Baltic Sea. Chemosphere 67, S90–S95.

Kemmlein, S., Hermeneit, A., Rotard, W., 2002. Carbon skeleton analysesof chloroparaffins in sediment, mussels and crabs. OrganohalogenCompds. 59, 279–282.

Kleinhenz, S., Jira, W., Schwind, K.H., 2006. Dioxin and polychlorinatedbiphenyl analysis: automation and improvement of clean-up estab-lished by example of spices. Mol. Nutr. Food Res. 50, 362–367.

Korytar, P., Parera, J., Leonards, P.E.G., Santos, F.J., de Boer, J.,Brinkman, U.A.Th., 2005. Characterization of polychlorinatedn-alkanes using comprehensive two-dimensional gas chromatogra-phy–electron-capture negative ionisation time-of-flight mass spectro-metry. J. Chromatogr. A 1086, 71–82.

Krauss, M., Wilcke, W., 2003. Polychlorinated naphthalenes in urbansoils: analysis, concentrations, and relation to other persistent organicpollutants. Environ. Pollut. 122, 75–89.

Lunden, C., Noren, K., 1998. Polychlorinated naphthalenes and otherorganochlorine contaminants in Swedish human milk. Arch. Environ.Contam. Toxicol. 34, 414–423.

Lundgren, K., Tysklind, M., Ishaq, R., Broman, D., van Bavel, B., 2002.Polychlorinated naphthalene levels, distribution, and biomagnificationin a benthic food chain in the Baltic Sea. Environ. Sci. Technol. 36,5005–5013.

Lundgren, K., Tysklind, M., Ishaq, R., Broman, D., van Bavel, B., 2003.Flux estimates and sedimentation of polychlorinated naphthalenes inthe northern part of the Baltic Sea. Environ. Pollut. 126, 93–105.

Malavia, J., Santos, F.J., Galceran, M.T., 2004. Gas chromatography–iontrap tandem mass spectrometry versus GC–high-resolution massspectrometry for the determination of non-ortho-polychlorinatedbiphenyls in fish. J. Chromatogr. A 1056, 171–178.

Mandalakis, M., Tsapakis, M., Stephanou, E.G., 2001. Optimization andapplication of high-resolution gas chromatography with ion traptandem mass spectrometry to the determination of polychlorinatedbiphenyls in atmospheric aerosols. J. Chromatogr. A 925, 183–196.

1562 P. Castells et al. / Chemosphere 70 (2008) 1552–1562

Manodori, L., Gambaro, A., Zangrando, R., Turetta, C., Cescon, P.,2006. Polychlorinated naphthalenes in the gas-phase of the VeniceLagoon atmosphere. Atmos. Environ. 40, 2020–2029.

Martı, I., Ventura, F., 1997. Polychlorinated naphthalenes in groundwatersamples from the Llobregat aquifer (Spain). J. Chromatogr. A 786,135–144.

Meijer, S.N., Harner, T., Helm, P.A., Crispin, J.H., Johnston, A.E., Jones,K.C., 2001. Polychlorinated naphthalenes in U.K. Soils: time trends,markers of source, and equilibrium status. Environ. Sci. Technol. 35,4205–4213.

Murray, T., Frankenberry, M., Steele, D.H., Heath, R.G., 1999. Chlo-rinated paraffins: a report on the findings from two field studies, SugarCreek, Ohio, Tinkers Creek, Ohio. Volume 1: Technical report.Washington DC, US Environmental Protection Agency, 150 pp (EPA-560/5-87/012).

Nicholls, C.R., Allchin, C.R., Law, R.J., 2001. Levels of short andmedium chain length polychlorinated n-alkanes in environmentalsamples from selected industrial areas in England and Wales. Environ.Pollut. 114, 415–430.

Nilsson, M.L., Waldeback, M., Liljegren, G., Kylin, H., Markides, K.E.,2001. Pressurized-fluid extraction (PFE) of chlorinated paraffins fromthe biodegradable fraction of source-separated household waste. Anal.Chem. 370, 913–918.

Noma, Y., Yamamoto, T., Sakai, S.I., 2004. Congener-specific composi-tion of polychlorinated naphthalenes, coplanar PCBs, dibenzo-p-dioxins, and dibenzofurans in the Halowax Series. Environ. Sci.Technol. 38, 1675–1680.

OSPAR. Action Plan 1998–2003, Annex 14, Meeting of the OSPARCommission, 1999.

Pan, J., Yang, Y.-L., Xu, Q., Chen, D.-Z., Xi, D.-L., 2007. PCBs, PCNsand PBDEs in sediments and mussels from Qingdao sea in the frame ofcurrent circulations and influence of sewage sludge. Chemosphere 66,1971–1982.

Parera, J., Santos, F.J., Galceran, M.T., 2002. Determination of chlori-nated paraffins in river sediments. Organohalogen Compds. 55, 195–198.

Persson, N.J., Gustafsson, O., Bucheli, T.D., Ishaq, R., Naes, K.,Broman, D., 2005. Distribution of PCNs, PCBs, and other POPstogether with soot and other organic matter in the marine environmentof the Grenlandsfjords, Norway. Chemosphere 60, 274–283.

Peters, A.J., Tomy, G.T., Jones, K.C., Coleman, P., Stern, G.A., 2000.Occurrence of C10–C13 polychlorinated n-alkanes in the atmosphere ofthe United Kingdom. Atmos. Environ. 34, 3085–3090.

Reth, M., Zencak, Z., Oehme, M., 2005. First study of congener grouppatterns and concentrations of short- and medium-chain chlorinatedparaffins in fish from the North and Baltic Sea. Chemosphere 58, 847–854.

Shojania, S., 1999. The enumeration of isomeric structures for polychlo-rinated N-alkanes. Chemosphere 38, 2125–2141.

Sobrado, C., Quintela, C., Blanco, L., Cabaleiro, S., Gonzalez, J.C.,Vieites, J.M., 2004. Suitability of an ion trap GC/MS/MS method forroutine analysis of PCDD/Fs in fishery products and by-products.Organohalogen Compds. 66, 369–376.

Sprovieri, M., Feo, M.L., Prevedello, L., Manta, D.S., Sammartino, S.,Tamburrino, S., Marsella, E., 2007. Heavy metals, polycyclic aromatichydrocarbons and polychlorinated biphenyls in surface sediments ofthe Naples harbor (southern Italy). Chemosphere 67, 998–1009.

Stejnarova, P., Coelhan, M., Kostrhounova, R., Parlar, H., Holoubek, I.,2005. Analysis of short chain chlorinated paraffins in sediment samplesfrom the Czech Republic by short-column GC/ECNI-MS. Chemo-sphere 58, 253–262.

Taniyasu, S., Falandysz, J., Swietojanska, A., Flisak, M., Horii, Y.,Hanari, N., Yamashita, N., 2005. Clophen A60 composition andcontent of CBs, CNs, CDFs, and CDDs after 2D-HPLC, HRGC/LRMS, and HRGC/HRMS separation and quantification. J. Environ.Sci. Health A 40, 43–61.

Tomy, G.T., Stern, G.A., Muir, D.C.G., Fisk, A.T., Cymbalisty, C.D.,Westmore, J.B., 1997. Quantifying C10–C13 polychloroalkanes inenvironmental samples by high-resolution gas chromatography/elec-tron capture negative ion high-resolution mass spectrometry. Anal.Chem. 69, 2762–2771.

Tomy, G.T., Stern, G.A., Lockhart, W.L., Muir, D.C.G., 1999a.Occurrence of C10–C13 polychlorinated n-alkanes in Canadian Mid-latitude and Arctic Lake sediments. Environ. Sci. Technol. 33, 2858–2863.

Tomy, G.T., Westmore, J.B., Stern, G.A., Muir, D.C.G., Fisk, A.T.,1999b. Interlaboratory study on quantitative methods of analysis ofC10–C13 polychloro-n-alkanes. Anal. Chem. 71, 446–451.

Villeneuve, D.L., Kannan, K., Khim, J.S., Falandysz, J., Nikiforov, V.A.,Blankenship, A.L., Giesy, J.P., 2000. Relative potencies of individualpolychlorinated naphthalenes to induce dioxin-like responses in fishand mammalian in vitro bioassays. Arch. Environ. Contam. Toxicol.39, 273–281.

Wafo, E., Sarrazin, L., Diana, C., Schembri, T., Lagadec, V., Monod,J.L., 2006. Polychlorinated biphenyls and DDT residues distribution insediments of Cortiou (Marseille, France). Marine Pollut. Bull. 52, 104–120.

Wang, D., Atkinson, S., Hoover-Miller, A., Li, Q.X., 2005. Analysis oforganochlorines in harbor seal (Phoca vitulina) tissue samples fromAlaska using gas chromatography/ion trap mass spectrometry by anisotopic dilution technique. Rapid Commun. Mass Spectrom. 19,1815–1821.

Wang, D., Atkinson, S., Hoover-Miller, A., Li, Q.X., 2007. Polychlori-nated naphthalenes and coplanar polychlorinated biphenyls in tissuesof harbor seals (Phoca vitulina) from the northern Gulf of Alaska.Chemosphere 67, 2044–2057.

Yamashita, N., Kannan, K., Imagawa, T., Miyazaki, A., Giesy, J.P.,2000a. Concentrations and profiles of polychlorinated naphthalenecongeners in eighteen technical polychlorinated biphenyl preparations.Environ. Sci. Technol. 34, 4236–4241.

Yamashita, N., Kannan, K., Imagawa, T., Villeneuve, D.L., Hashimoto,S., Miyazaki, A., Giesy, J.P., 2000b. Vertical profile of polychlorinateddibenzo-p-dioxins, dibenzofurans, naphthalenes, biphenyls, polycyclicaromatic hydrocarbons, and alkylphenols in a sediment core fromTokyo Bay, Japan. Environ. Sci. Technol. 34, 3560–3567.

Yusa, V., Pardo, O., Pastor, A., de la Guardia, M., 2006. Optimization ofa microwave-assisted extraction large-volume injection and gas chro-matography–ion trap mass spectrometry procedure for the determi-nation of polybrominated diphenyl ethers, polybrominated biphenylsand polychlorinated naphthalenes in sediments. Anal. Chim. Acta 557,304–313.

Zencak, Z., Reth, M., Oehme, M., 2004. Determination of totalpolychlorinated n-alkane concentration in biota by electron ioniza-tion-MS/MS. Anal. Chem. 76, 1957–1962.