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  • Environmental Pollution 131 (2004) 13e24

    www.elsevier.com/locate/envpol

    Polycyclic aromatic hydrocarbon composition in soilsand sediments of high altitude lakes

    Joan O. Grimalta,*, Barend L. van Droogea, Alejandra Ribesa,Pilar Fernándeza, Peter Applebyb

    aDepartment of Environmental Chemistry, Institute of Chemical and Environmental Research (ICER-CSIC),

    Jordi Girona 18-26, 08034 Barcelona, Catalonia, SpainbDepartment of Mathematical Sciences, University of Liverpool, P.O. Box 147, Liverpool L69 3BX, UK

    Received 4 September 2003; accepted 9 February 2004

    ‘‘Capsule’’: The concentrations of polycyclic hydrocarbons in soils are more stronglycorrelated with deposition rate than the concentrations in sediments.

    Abstract

    Polycyclic aromatic hydrocarbons (PAH) in lake sediments and nearby soils of two European high mountain regions, Pyrenees

    and Tatra, have been studied. Similar mixtures of parent PAH were observed in all cases, indicating predominance of airbornetransported combustion products. Nevertheless, the composition of these atmospherically long-range transported PAH was betterpreserved in the superficial layers of soils than sediments. This difference points to significant PAH degradation process, e.g. during

    lake water column transport, before accumulation in the latter. Post-depositional transformation was also different in both types ofenvironmental compartments. Thus, lake sediments exhibit higher preservation of the more labile PAH involving lower degree ofpost-depositional oxidation. However, they also show the formation of major amounts of perylene by diagenetic transformation in

    the deep sections. This compound is not formed in soils where downcore enrichments of phenanthrene are observed, probably asa consequence of diagenetic aromatization of diterpenoids.� 2004 Elsevier Ltd. All rights reserved.

    Keywords: Polycyclic aromatic hydrocarbons; High maintain areas; Soil pollution; Lake pollution; Long-range transported pollutants; Combustion

    pollution

    1. Introduction

    PAH in the environment deserve increasing attentionfor their widespread occurrence and mutagenic, carci-nogenic and teratogenic effects (Freitag et al., 1985).They may be generated from organic matter diagenesisand anthropogenic processes (Simoneit, 1977; La-Flamme and Hites, 1978; Wakeham et al., 1980a,b).However, the anthropogenic contribution usually out-weighs the inputs from other sources and is responsiblefor their general increase over the last 100 yr (Hiteset al., 1977; Fernández et al., 2000).

    * Corresponding author. Tel.: C34-93-4006122; fax: C34-93-

    2045904.

    E-mail address: [email protected] (J.O. Grimalt).

    0269-7491/$ - see front matter � 2004 Elsevier Ltd. All rights reserved.doi:10.1016/j.envpol.2004.02.024

    Depending on their physico-chemical properties,atmospheric PAH are distributed between the gas andparticulate phases, mainly in association with smallparticles (!1 mm) (Aceves and Grimalt, 1993; Mascletet al., 1988; Allen et al., 1996; Ribes et al., 2003). Theyare transported through the atmosphere to remotesites giving rise to a general background level in soils(Hartmann, 1996; Wilcke and Zech, 1997; Wild andJones, 1995; Vogt et al., 1987; Berteigne et al., 1988; Joneset al., 1989a,b; Guggenberg et al., 1996; Wilcke et al.,1996) and lake sediments (LaFlamme and Hites, 1978;Gschwend and Hites, 1981; Atlas et al., 1981; Simciket al., 1996; Fernández et al., 1996, 1999, 2000) where theyaccumulate due to their high stability and small mobilityas a consequence of their low water solubility. Soilsand lake sediments are therefore good environmental

    mailto:[email protected]://www.elsevier.com/locate/envpol

  • 14 J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    compartments to record the historical environmentalburden of these compounds as a consequence of humanactivities.

    In this respect, European high mountain lakes havebeen observed to accumulate significant loads ofatmospherically transported PAH despite their remote-ness (Fernández et al., 1996, 1999, 2000; Carrera et al.,2001; Vilanova et al., 2001). These lakes are definedas those situated above the local tree line, far from anypollution source and lacking major water inputs fromthe catchment. They constitute unique environments forthe assessment of the atmospheric pollution load overcontinental areas. Geographical and historical patternsof this pollution load in Western Europe have beendescribed recently based on the study of sediments fromthese lakes (Fernández et al., 1999, 2000). However,PAH not only accumulate in lake sediments but also inother environmental compartments such as soils. Aglobal understanding of their overall burden in thesehigh mountain areas also requires the study of thiscompartment.

    High mountain areas are therefore ideal environmentsfor comparison of PAH accumulation in soils and lakesediments since both compartments are under thesame atmospheric precipitation fluxes. Accordingly, thePyrenees and the Tatra mountains have been selected forthe study of PAH in lake sediments and nearby soils.

    The Pyrenees is a mountain range where moderatepollution levels by PAH have been recorded (Fernándezet al., 1999, 2000). Lake Redon (42(38#34$N,0(46#13$E; 2240 m above sea level; Fig. 1) is the largesthigh mountain lake in this area (24 ha) and has been usedas reference lake for many environmental studies. Twolake sediment cores and two soil cores collected nearbythe lake are considered in the present study. The sedimentcores, A andB, were retrieved from the deeper parts of thetwobasins, 73 and 32 mwater columndepth, respectively.

    The Tatra mountains are situated in central Europeand constitute one of the most polluted mountain rangefor these compounds (Fernández et al., 1999, 2000). Twosoil and one sediment cores from Ladove Lake(49(11#03$N, 20(09#46$E; 2057 m) were collected. The

    49° 30'

    49° 15'

    49° 00'

    49° 30'

    49° 15'

    49° 00'

    19°

    50°

    48°

    46°

    44°

    42°

    50°

    48°

    46°

    44°

    42°

    0° 5° 10° 15° 20°

    0° 5° 10° 15° 20°

    20° 21°

    19° 20° 21°

    Redon

    Dlugi staw

    Starolesnianske pleso

    Ladove

    Mountain

    Tatra

    Fig. 1. Map showing the location of the soils and sediments sampled in high mountain European regions. Pyrenees, Redon (soils and sediments).

    Tatra, Ladove (soils and sediments), Dlugi Staw and Starolesnianske Pleso (sediments).

  • 15J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    sediment core is compared to others collected in lakesfrom the same mountain range such as StarolesnianskePleso (49(10#48$N, 20(10#4$E; 2000 m) and DlugiStaw (49(13#36$N, 20(0#39$E; 1783 m) (Fig. 1). LakesLadove and Starolesnianske Pleso are situated less than2 km apart.

    To the best of our knowledge, this is the first studycomparing the distribution of PAH in soils and lakesediments, particularly in high mountain areas.

    2. Materials and methods

    2.1. Materials

    Residue analysis n-hexane, dichloromethane, isooc-tane, methanol and acetone were from Merck (Darm-stadt, Germany). Anhydrous sodium sulfate for analysiswas also from Merck. Neutral aluminum oxide type507Cwas fromFlukaAG (Buchs, Switzerland). Celluloseextraction cartridges were from Whatman Ltd (Maid-stone, England). Aluminum foil was rinsed with acetoneand let to dry at ambient temperature prior to use. Thepurity of the solvents was checked by gas chromatogra-phy-mass spectrometry (GC-MS). No significant peaksshould be detected for acceptance. Aluminum oxide,sodium sulfate and cellulose cartridges were cleaned bySoxhlet extractionwith hexane:dichloromethane (4:1, v/v)during 24 h before use. The purity of the cleaned reagentswas checked by ultrasonic extraction with n-hexane:dichloromethane (4:1;3! 20 mL), concentration to50 mL and analysis by GC-MS. No interferences weredetected. Sodium sulfate and aluminum oxide wereactivated overnight at 400 (C and 120 (C, respectively.

    2.2. Sampling

    Sediment samples were taken in the deepest points ofthe lakes using a gravity coring system (Glew, 7.5 cmdiameter, 30 cm long). A 7 cm (diameter)! 20 cm(long) stainless steel cylinder was used for soil corecollection. All soils were taken within the lake catch-ment areas. The sediment samples except those fromLadove Lake were collected between 1993 and 1994whereas the soil cores and the sediments from LadoveLake were sampled in 2001. Immediately after sam-pling, soil and sediment cores were divided in sections of2 and 0.5 cm, respectively (0.3 and 0.25 cm in the case ofRedon and Ladove sediments, respectively), and storedin pre-cleaned aluminum foil at �20 (C until analysis.

    2.3. Analysis

    The following PAHs were determined in both soilsand sediments: acenapthene, acenaphtylene, fluo-rene, phenanthrene, anthracene, dibenzothiophene,

    methylphenanthrenes (3-MPhe, 2-MPhe, 9C 4-MPhe,1-MPhe), methyldibenzothiophenes (4-MDBT, 3C2-MDBT, 1-MDBT), fluoranthene, pyrene, dimethyl-phenanthrenes (3,6-DMPhe, 2,6-DMPhe, 2,7-DMPhe,1,3C 2,10C 3,9C 3,10-DMPhe, 1,6C 2,9-DMPhe,1,7-DMPhe, 2,3-DMPhe, 1,9C 4,9-DMPhe, 1,8-DMPhe), retene, benzo(b)naphtho[2,1-d]thiophene, benz[a]anthracene, chryseneC triphenylene (they coelutedupon GC-MS analysis so they were considered together),benzo[bC j]fluoranthenes, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, perylene, indeno[1,2,3-cd]pyrene, benzo[ghi]perylene, dibenz[a,h]anthracene andcoronene.

    2.4. Sample extraction

    Soils (25e50 g) were weighed into aWhatman Soxhletcellulose thimble. About 1:1 w/w sodium sulfate weremixedwith the soil in order to improve Soxhlet extractionby water removal. Samples were extracted with hexane:dichloromethane (4:1) for 18 h. Standards of d10-anthra-cene, d10-pyrene, d12-benz[a]anthracene and d12-benzo[ghi]perylene were added to the extracts that were firstconcentrated by rotary vacuum evaporation to 3e5 mLand subsequently eluted through a drying column filledwith 1 g of anhydrous sodium sulfate.

    After rotary vacuum evaporation to w0.5 mL, theextracts were fractionated on a neutral aluminum oxidecolumn (2 g). A first non-polar fraction was obtainedby elution with 8 mL of hexane:dichloromethane(9:1). The second, obtained by elution with 10 mL ofhexane:dichloromethane (1:2), corresponded to the frac-tion of PAHs and other aliphatic esters. This PAHfraction was then hydrolyzed overnight with KOHin methanol for removal of the aliphatic esters. Neu-tral compounds were recovered with n-hexane andfractionated again by adsorption chromatography withaluminum oxide (2 g). After elution with hexane:dichloromethane (1:2), the PAH fraction was concen-trated to 50 mL in isooctane by rotary vacuum evapora-tion followed by a gentle stream of purified N2.

    For sediments, about 0.1e1 g of wet sediment wasextracted by sonication with methanol (1! 20 mL;20 min) in order to separate most of the interstitial waterfrom the sediment. The subsequent extractions wereperformed with (2:1, v/v) dichloromethaneemethanol(3! 20 mL; 20 min). All extracts were combinedand spiked with deuterated PAH internal standards(d10-anthracene, d10-pyrene, d12-benz[a]anthracene andd12-benzo[ghi]perylene). Then, they were vacuum evap-orated to almost 10 mL and hydrolyzed overnight with20 mL of 6% (w/w) KOH in methanol. The neutralfractions were recovered with n-hexane (3! 10 mL),vacuum evaporated to almost dryness, and fractionatedwith a column containing 2 g of alumina. The aromaticfractions (10 mL of dichloromethane: n-hexane, 2:1) were

  • 16 J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    vacuum evaporated to 500 mL and nitrogen concentratedalmost to dryness and redissolved in isooctane prior toGC-MS analysis.

    2.5. Instrumental analysis

    The internal standard d12-perylene (L.D. Ehrenstor-fer) was added to the vials prior to injection. Sampleswere injected into GC-MS (Fisons 8000 Series, MassSelective Detector 800 Series). A fused silica capillarycolumn, HP-5 of 50 m and 0.25 mm i.d. (0.25 mm filmthickness) was used. The oven temperature programstarted at 90 (C (1 min hold), followed by a 4(/min rampup to 300 (C (15 min hold). Injector, transfer line and ionsource temperatures were 280 (C, 300 (C and 200 (C,respectively. Helium was used as carrier gas (1.1 mL/min). PAH were determined in the electron impact andselected ion recording modes. The following mass frag-ments were used for identification and quantification:m/z166, 178, 184, 192, 202, 206, 219, 226, 228, 234, 252, 276,278, and 300 (dwell time 40 ms per single ion, ion windowaccording to retention times of standards). Diagnosticions of the corresponding perdeuterated standards m/z:188, 212, 240, 264, and 288 were also used.

    2.6. Quantification

    Quantification was performed by combination of theexternal standard (EPA, Mix 9 Dr Ehrenstorfer) andretention index methods. Calibration curves (detectorresponse vs amount injected) were performed for eachcompound. The range of linearity of the detector wasevaluated from the curves generated by representationof detector signal/amount injected vs amount injected.All measurements were performed in the ranges oflinearity found for each compound. The quantitativedata were corrected for surrogate recoveries.

    2.7. Quality control

    Procedural blanks were performed with each set ofnine samples to check for the presence of interferingpeaks. Recoveries of d10-anthracene, d10-pyrene, d12-benz[a]anthracene and d12-benzo[ghi]perylene averaged60, 70, 76 and 82%, respectively. Replicate analysis ofsoil samples gave an error !G 15%. The methoddetection limits based on signal to noise ratio of 3 in realsamples ranged from 100 (compound) to 400 pg(compound). Both soil and sediment analytical proce-dures were successfully calibrated with a standardreference material with certified PAH values (marinesediment HS-4, Institute for Marine Biosciences, Cana-dian National Research Council).

    2.8. Total organic carbon

    Soil and sediment samples were treated with HCl 3 Nto remove inorganic carbon. Subsequently, they werecleaned with Milli-Q water until neutral pH (7G 0:2)and dried at 60 (C. The determination of TOC wasperformed by flash combustion at 1025 (C followed bythermic conductivity detection in a CHNS ElementalAnalyser EA1108. The limit of detection was 0.1%.

    2.9. Radiometric dating

    Sediment and soil samples were analysed for 210Pb,226Ra, 137Cs and 241Am by direct gamma assay usingOrtec HPGe GWL series well-type coaxial low back-ground intrinsic germanium detectors (Appleby et al.,1986). 210Pb was determined via its gamma emissions at46.5 keV and 226Ra by the 295 keV and 352 keV g-raysemitted by its daughter isotope 214Pb following 3 weeksstorage in sealed containers to allow radioactiveequilibration. 137Cs and 241Am were measured by theiremissions at 662 keV and 59.5 keV. The absoluteefficiencies of the detectors were determined usingcalibrated sources and sediment samples of knownactivity. Corrections were made for the effect of self-absorption of low energy g-rays within the sample(Appleby et al., 1992). Supported 210Pb activity wasassumed to be equal to the measured 226Ra activity.Unsupported 210Pb activity was calculated by subtract-ing supported 210Pb from the measured total 210Pbactivity. 210Pb radiometric dates were calculated usingthe CRS and CIC dating models (Appleby and Oldfield,1978) where appropriate and validated where possibleagainst the 1986 and 1963 depths determined from the137Cs/241Am stratigraphic records.

    3. Results and discussion

    3.1. Lake features

    The lakes considered in this study are situated abovethe local tree line, they are oligotrophic (median totalphosphorous 4.1 mg/L) and remain ice-covered for longperiods. Three dominant types of land cover are foundin the lake catchments, dry alpine meadows, morainesand solid rock. Among these, the former were selectedfor study. Soils in the dry alpine meadows are mostlyundeveloped (e.g. leptosol, podsol and histosol) withaverage mineral horizons of about 33 cm thickness andshallow organic matter horizons (5e17 cm, average4 cm). These soils are covered by grass in summer andunder snow during the cold months (Catalan, 1988).Pollution inputs are related to atmospheric transportsince the lakes are free from local anthropogenicsources. Nevertheless, significant differences in pollution

  • 17J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    Table 1

    Average PAH concentrations, PAH ratios and TOC in the soil and sediment cores from Lake Redon

    0e2 cm 2e4 cm 4e6 cm 6e8 cm 8e10 cm 10e12 cm

    Soils

    Parent PAHa 770 670 190 34 39 47

    Fla/(PyrC Fla) 0.61 0.58 0.54 0.54 0.57 0.56

    BaA/(BaACCCT) 0.21 0.24 0.24 0.17 0.11 0.19BaP/(BaPCBeP) 0.32 0.35 0.39 0.37 0.34 0.43

    Ind/(IndCBghi) 0.55 0.57 0.56 0.56 0.55 0.56

    SUM MPhe/(SUM MPheC Phe) 0.45 0.56 0.59 0.28 0.46 0.48

    Ret/(RetC BNT) 0.32 0.01 0.45 0.89 0.58 0.351,7-/(1,7-C 2,6-)DMPhe 0.70 0.67 0.62 0.77 0.67 0.62

    TOC (g/g dw) 0.33 0.30 0.23 0.18 0.16 0.21

    Sedimentsb

    Parent PAHa 760 550 100 130 87

    Fla/(PyrC Fla) 0.65 0.68 0.59 0.57 0.67

    BaA/(BaACCCT) 0.16 0.13 0.12 0.12 0.12

    BaP/(BaPCBeP) 0.20 0.20 0.25 ec eInd/(IndCBghi) 0.62 0.63 0.64 0.78 0.69

    SUM MPhe/(SUM MPheC Phe) 0.33 0.58 0.47 0.44 0.20

    Ret/(RetC BNT) 0.21 0.28 0.85 e 0.74

    1,7-/(1,7-C 2,6-)DMPhe 0.56 0.62 0.63 0.49 0.67TOC (g/g dw) 0.04 0.04 0.05 0.04 0.04

    a Units in ng/g dry weight. These values correspond to the sum of all compounds indicated in the caption of Fig. 2 except perylene.b Core B.c Not determined because of interferences from the huge amount of perylene.

    load are observed in both lake groups since much higherPAH levels are encountered in Tatra mountains(Fernández et al., 1999, 2000).

    TOC exhibits much higher values in the soils than inthe sediments of Lake Redon, 16e33% and 4e5%, re-spectively (Table 1). In Ladove lake, higher TOC valuesare also found in soils than sediments in the upper 6 cm,12e23% and 7e8.3%, respectively (Table 2). However,

    between 6e8 cm the difference between the two envi-ronmental compartments vanishes, 7% in both cases(Table 2). A strong depth-dependent TOC decrease istherefore observed in Ladove soils whereas sedimentaryTOC remains nearly constant. In Lake Redon, soil TOCvalues also decrease significantly with depth, from 33%to 16e21%, whereas the sediment values are nearlyconstant (Table 1).

    Table 2

    Average PAH concentrations, PAH ratios and TOC in the soil and sediment cores from Ladove lake

    Core sections 0e2 cm 2e4 cm 4e6 cm 6e8 cm 8e10 cm 10e12 cm

    Soils

    Parent PAHa 1900 3400 430 75 63 90

    Fla/(PyrC Fla) 0.71 0.54 0.57 0.61 0.52 0.50

    BaA/(BaACCCT) 0.32 0.23 0.14 0.13 0.11 0.13

    BaP/(BaPCBeP) 0.42 0.39 0.27 0.18 0.31 0.26Ind/(IndCBghi) 0.53 0.47 0.39 0.30 0.47 0.46

    SUM MPhe/(SUM MPheC Phe) 0.34 0.37 0.78 0.48 0.18 0.25

    Ret/(RetC BNT) 0.29 0.02 0.02 0.05 0.14 0.041,7-/(1,7-C 2,6-)DMPhe 0.79 0.63 0.77 0.79 0.56 0.59

    TOC (g/g dw) 0.23 0.16 0.12 0.07 0.07 0.07

    Sediments

    Parent PAHa 12,000 11,000 3000 3000

    Fla/(PyrC Fla) 0.62 0.61 0.60 0.59

    BaA/(BaACCCT) 0.18 0.18 0.17 0.19

    BaP/(BaPCBeP) 0.30 0.28 0.29 0.30Ind/(IndCBghi) 0.56 0.56 0.54 0.53

    SUM MPhe/(SUM MPheC Phe) 0.26 0.25 0.27 0.25

    Ret/(RetC BNT) 0.03 0.06 0.14 0.22

    1,7-/(1,7-C 2,6-)DMPhe 0.61 0.62 0.68 0.79TOC (g/g dw) 0.08 0.07 0.07 0.07

    a Units in ng/g dry weight. These values correspond to the sum of all compounds indicated in the caption of Fig. 2 except perylene.

  • 18 J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    SEDIMENTS SOILS

    B AA B

    mc 3.0-0

    0

    002

    004

    mc 9.0-6.0

    0001002003

    mc 2.1-9.0

    0001002003

    mc 2.4-6.3

    0

    0005

    00001

    7151311197531

    mc 5.0-0

    005001051

    mc 5-5.4

    05.015.1

    mc 6-5.5

    0

    5

    01

    mc 7-5.6

    0

    02

    04

    mc 9-8

    0

    05

    001

    mc 91-81

    0

    001

    002

    7151311197531

    mc 2-0

    0020406

    mc 2-0

    0002004006

    mc 4-2

    005001051

    mc 4-2

    0

    001

    002

    mc 6-4

    0020406

    mc 6-4

    0010203

    mc 8-6

    0

    01

    02mc 8-6

    0

    01

    02

    mc 01-8

    050151

    mc 01-8

    050151

    mc 21-01

    0

    01

    02

    7151311197531

    mc 21-01

    050151

    7151311197531

    Fig. 2. PAH in the soils and sediments from Lake Redon. A and B refer to different cores analysed in the lake surroundings. 1, fluorene; 2,

    phenanthrene; 3, anthracene; 4, fluoranthene; 5, pyrene; 6, retene; 7, benz[a]anthracene; 8, chryseneC triphenylene; 9, benzo[bC j]fluoranthenes; 10,

    benzo[k]fluoranthene; 11, benzo[e]pyrene; 12, benzo[a]pyrene; 13, perylene; 14, indeno[1,2,3-cd]pyrene; 15, benzo[ghi]perylene; 16, dibenz[a,h]an-

    thracene, 17, coronene. PAH units in ng/g.

    3.2. PAH distributions

    The PAH distributions found in the sediments andsoils of the Pyrenees and Tatra lakes are shown inFigs. 2 and 3. The distributions are always dominatedby parent PAH, from phenanthrene to coronene, witha predominance of high molecular weight compounds

    of catacondensed structures in the upper sections.Total methylatedC dimethylated PAH were in lowamounts (0.2e10% of total PAH).

    The PAH distributions in the sediments fromPyrenees and Tatra mountains are remarkably similardespite the variability of PAH sources to the atmo-sphere. This similarity is also observed independently of

    SENTIMENTS SOILS

    LADOVE STAR DLUGI A B

    mc 5.0-0

    0000100020003

    mc 52.0-0

    0

    05

    001

    mc 2-57.1

    0000100020003

    mc 2-0

    0

    0002

    0004mc 2-0

    0000100020003

    mc 4-2

    000500010051

    mc 4-2

    0002004006

    mc 6-4

    005001051

    mc 6-4

    005001051

    mc 8-6

    0

    01

    02mc 8-6

    0

    02

    04

    mc 21-01

    0

    01

    02

    7151311197531

    mc 21-01

    0

    02

    04

    7151311197531

    mc 52.3-3

    0000100020003

    mc 52.4-4

    0002004006

    mc 57.7-5.7

    0002004006

    7151311197531

    mc 5.2-2

    0

    0001

    0002

    mc 5.5-5

    0002004006

    mc 31-21

    005001051

    mc 81-71

    005001051

    7151311197531

    mc 5.0-0

    0

    0001

    0002

    mc 5.2-2

    000500010051

    mc 5.4-4

    0002004006

    mc 6-5.5

    0001002003

    mc 9-8

    005001051

    7151311197531

    Fig. 3. PAH in the soils and sediments from Ladove lake. Numbers in abscissas as in Fig. 2. PAH units in ng/g.

  • 19J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    the high differences in PAH load between the Pyreneesand Tatra which, in terms of sedimentary concentra-tion, involve top sediment concentrations of 980 and12,000 ng/g total PAH, respectively (Tables 1 and 2).This uniform sedimentary PAH profile exhibits a highparallelism with the PAH composition in the atmo-spheric aerosols collected at these high altitude sites(Fernández et al., 2002). This PAH distribution is quiteubiquitous and has been reported in sediments fromremote/rural areas (Sanders et al., 1993; Tolosa et al.,1996; Fernández et al., 1999, 2000) and corresponds tothe airborne combustion mixtures refractory to photo-oxidation and chemical degradation (Simcik et al., 1996;Simó et al., 1997).

    The soil PAH mixtures also exhibit a predominanceof parent PAH in which the heavier molecular weightcompounds are present in higher relative proportion(Figs. 2 and 3). However, the qualitative and quanti-tative differences between soil cores from the same areaare higher. Thus, the top distributions in the Tatralakes exhibit high relative concentrations of chryseneCtriphenylene, benzo[bC j]fluoranthenes, benzo[k]fluor-anthene, benzo[e]pyrene and benzo[a]pyrene in bothcores. Nevertheless, one of them, B (Fig. 3), also hasbenz[a]anthracene, perylene, indeno[1,2,3-cd]pyrene,benzo[ghi]perylene, dibenz[a,h]anthracene and coronenein high relative proportion. These compounds are not sosignificant in core A (Fig. 3). The PAH top soildistributions of Lake Redon are also dominated bybenzo[bC j]fluoranthenes, benzo[k]fluoranthene, benzo[e]pyrene and benzo[a]pyrene but in one case, A (Fig. 2),phenanthrene, fluoranthene and pyrene are also presentin significant relative concentration.

    3.3. Regular differences in soil andsediment PAH composition

    The PAH ratios of some soil and sediment sectionsfrom Redon and Ladove lakes are compared in Tables 1and 2. The ratios are grouped in core sections only forcomparison of the vertical PAH structure. The groupingdoes not involve temporal correspondences between thesame soil and sediment depth levels.

    The benz[a]anthracene/(benz[a]anthraceneC chry-seneC triphenylene) ratios from the upper core sectionsexhibit higher values in the soils than in the sediments.Thus, in Lake Redon (0e8 cm) the differences rangebetween 0.17e0.24 in the former case and between0.12e0.15 in the second (Table 1). In Ladove lake(0e4 cm) the values span between 0.23e0.32 in soilsand exhibit a constant ratio of 0.18 in the sediments(Table 2).However, in the deeper sections the ratios of thesoil values are lower, e.g. 0.11 and 0.12 for soils andsediments of Lake Redon (8e10 cm), respectively(Table 1), and 0.13e0.14 and 0.17e0.19 for the soils

    and sediments of Ladove lake (4e8 cm), respectively(Table 2).

    Benz[a]anthracene is more labile to photooxidationthan chrysene C triphenylene (Kamens et al., 1986,1988). Accordingly, the benz[a]anthracene/(benz[a]anthraceneC chryseneC triphenylene) ratio in atmo-spheric aerosols collected over high mountain lakes hasaverage values of 0.12 in summer and 0.35 in winter(Fernández et al., 2002). Having in mind that PAH arepresent in higher concentration in the winter samples(Fernández et al., 2002), the soil ratios in the topsections of the soil cores are likely more representativeof the PAH atmospheric fallout. Benz[a]anthracene isalso less stable than chryseneC triphenylene upondiagenesis since the highest relative content in theformer is generally encountered in the top core layers.The difference between soils and sediments suggests thatthe original atmospherically transported PAH compo-sition is initially better preserved in the soils (upper coresections) but at deeper core sections the benz[a]anthra-cene/(benz[a]anthraceneC chryseneC triphenylene) ra-tio deviates further from the original mixtures in soilsthan sediments.

    Benzo[a]pyrene is photochemically less stable thanbenzo[e]pyrene (Nielsen, 1988). In the top cores(0e4 cm) the benzo[a]pyrene/(benzo[a]pyreneCbenzo[e]pyrene) ratios show higher values in the soils than in thesediments. Thus, in Lake Redon, they range between0.32e0.35 and 0.22e0.23, respectively (Table 1), and inthe Tatra lakes between 0.39e0.42 and 0.28e0.30,respectively (Table 2).

    The benzo[a]pyrene/(benzo[a]pyreneC benzo[e]pyrene)ratios in aerosols collected in high mountain regionsaverage 0.27 in summer and 0.41 in winter (Fernándezet al., 2002). Again, considering the higher PAH loadin winter than in summer the soil values are more likelyto reflect better the original PAH atmospheric composi-tion. At deeper core sections no significant change isobserved in the sediments, e.g. 0.25 and 0.29e0.30in Redon and Ladove, respectively. Similarly, the deepersoil sections of Lake Redon exhibit ratios between 0.34and 0.43 (Table 1). However, in Ladove soils the deepsection ratios show larger scatter and lower values(0.18e0.31; Table 2). In some deeper soil sectionsthe benzo[a]pyrene/(benzo[a]pyreneC benzo[e]pyrene)ratios are even lower than those of sediments showingthat benzo[a]pyrene is less preserved in the former thanthe latter.

    The ratio between phenanthrene and its methylderivatives is also labile to photooxidation, the trans-formation involving a loss of methylated compoundsupon long-range transport (Simó et al., 1997). Compar-ison of the methylphenanthrenes/(methylphenanthre-nesC phenanthrene) ratio in soils and sedimentsshows ranges between 0.28e0.59 and 0.20e0.47, re-spectively, in Lake Redon (Table 1), and between

  • 20 J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    0.18e0.78 and 0.25e0.30, respectively, in Ladove lake(Table 2). In all cases except one section of Lake Redon(6e8 cm) the ratio is higher in the soil than in thesediments showing a better preservation of the morelabile compounds in the former.

    The indeno[1,2,3-cd]pyrene/(indeno[1,2,3-cd]pyreneCbenzo[ghi]perylene) ratio is a priori more stable tophotooxidation than the ratios discussed above. InRedon it ranges between 0.55e0.57 and 0.62e0.78in soils and sediments, respectively (Table 1), and inLadove lake between 0.30e0.53 and 0.53e0.56 in soilsand sediments, respectively (Table 2). The measuredrange in high mountain aerosols is 0.55 in both winterand summer (Fernández et al., 2002). These values areagain closer to the soil than to the sediment values inLake Redon. In contrast, in Ladove lake there isa higher difference between the atmospheric ratio andthose in soils than in sediments. There is no obviousexplanation for this deviation although it must beindicated that the aerosol values taken as reference(Fernández et al., 2002) correspond to a series of dataincluding atmospheric samples from Lake Redon butnot from the Tatra mountains.

    The fluoranthene/( fluorantheneC pyrene) ratios insoils range between 0.54e0.61 and 0.50e0.71 in LakesRedon and Ladove. In the sediments they range between0.59e0.66 and 0.59e0.62 at these two sites, respectively(Tables 1 and 2). The average values of this ratio in thehigh mountain aerosols are 0.44 in summer and 0.59 inwinter (Fernández et al., 2002). The winter values arecloser to those in the soils than in the sediments fromLake Redon but in Ladove lake the sediment values arethe closest to this mountain aerosol winter ratio. Inany case the differences between soils and sedimentsare small in the case of fluoranthene/( fluorantheneCpyrene) ratios.

    3.4. Downcore sedimentary PAH

    Radiometric analysis shows that all lake sedimentcores selected for study have rather uniform sedimen-tation. No hiatus or periods of mixing were observed inthe vertical structure of the recovered sediments. Theaverage sedimentation rates of the sediment coresstudied were 0.024, 0.054, 0.084 and 0.10 cm/yr forRedon, Dlugi Staw, Starolesnianske Pleso and Ladove.These rate differences and the core sectioning foranalysis provide vertical PAH profiles with differenttime resolutions at each site.

    The best time resolved PAH trend is the one forLadove Lake where biannual resolution is achieved inmost core sections between 1924 and 2001 (Fig. 4). Totalpyrolytic PAH were maxima between 1980 and 1988.Another period of maximum PAH input was observedbetween 1963e1966. Before this time, 1924e1954, muchlower PAH concentrations are observed. On the other

    hand, after the 1988 PAH maximum, a strong decreasein PAH concentrations is found which extends up to2001 (the most recent recorded date in the sedimentcollected). This PAH decrease is consistent with theimprovement of the combustion techniques in centralEurope.

    The pyrolytic PAH in the other lakes from the Tatramountains exhibit similar profiles but with smallertemporal resolution. As these cores were taken in1993, the most recent PAH decrease is not observed.Pyrolytic PAH in the sediment core of Lake Redon alsoexhibit a similar temporal trend. Like in the sedimentsfrom Dlugi Staw and Starolesnianske Pleso, the tem-poral resolution is lower than in Ladove lake and themost recent date recorded is 1994.

    Representation of the temporal changes of the majorparent PAH such as fluoranthene, benz[a]anthracene,chryseneC triphenylene, benzo[a]pyrene, benzo[e]pyr-ene and many others shows the same trends as for thetotal pyrolytic PAH. Perylene is also showing the sametemporal trend as the major pyrolytic PAH in the lakesfrom the Tatra mountains. However, in Lake Redon thehighest values are observed at deep core sections. Thus,the downcore changes in PAH may reflect the atmo-spheric inputs of these compounds arriving to the highmountain areas through time or in situ diageneticprocesses involving the formation of some PAH suchas perylene in Lake Redon.

    Retene is the compound exhibiting a more distinctbehavior with time. Their downcore profiles do notshow a steeper decrease since the concentrations in theancient core sections are not too different from those inwhich highest total pyrolytic inputs are found.

    3.5. Diagenetic formation of PAH

    In Lake Redon, PAH qualitative distribution in thedeeper sections show a high predominance of perylene,sections 0.9e4.2 cm in core A and 8e19 cm in core B(Fig. 2). This predominance also involves a net peryleneconcentration increase in both cores revealing in situformation of this PAH, e.g. in the deeper sections ofcore A it reaches more than 6000 ng/g which is higherthan all other PAH in all the other core sections (Fig. 2).In the Tatra mountains this trend is not observed (Figs.3 and 4). Only in the deeper sections of StarolesnianskePleso core a predominance of perylene is observed butwithout absolute concentration increase (Fig. 4).

    The predominance of perylene in ancient sedimentlayers of freshwater (Wakeham et al., 1980a; Tan andHeit, 1981) and marine systems (Aizenshtat, 1973;Wakeham et al., 1979; Venkatesan, 1988) has beenreported in the literature but its precursor/s still remainunknown. The downcore profiles observed in LakeRedon are consistent with an in situ production fromsedimentary precursor/s which, considering the high

  • STAROLESNIANSKE

    REDON DLUGI STAW PLESO LADOVE

    1821185118811911194119712001

    0 5000 10000 15000 20000

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    0 20 40

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    60

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    CHRYSENE+TRIPHENYLENE

    1821185118811911194119712001

    0 200 400 600

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    1821185118811911194119712001

    0 500 1000 1500

    BENZO(e)PYRENE

    1821185118811911194119712001

    0 5 10 15 20

    RETENE

    1821185118811911194119712001

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    PYROLYTIC PAH

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    FLUORANTHENE

    1821185118811911194119712001

    0 200 400 600

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    1821185118811911194119712001

    0 1000 2000 3000

    CHRYSENE+TRIPHENYLENE

    1821185118811911194119712001

    0 200 400 600 800

    BENZO(a)PYRENE

    1821185118811911194119712001

    0 500 1000 1500

    BENZO(e)PYRENE

    1821185118811911194119712001

    0 5 10 15

    RETENE

    1821185118811911194119712001

    0 5000 10000 15000 20000

    PYROLYTIC PAH

    1821185118811911194119712001

    0 500 1000 1500 2000

    FLUORANTHENE

    1821185118811911194119712001

    0 200 400

    BENZ(a)ANTRACENE

    1821185118811911194119712001

    0 500 1000 1500 2000

    CHRYSENE+TRIPHENYLENE

    1821185118811911194119712001

    0 200 400 600

    BENZO(a)PYRENE

    1821185118811911194119712001

    0 500 1000 1500

    BENZO(e)PYRENE

    1821185118811911194119712001

    0 1 2 3 4 5

    RETENE

    1821185118811911194119712001

    0 1000 2000 3000

    PYROLYTIC PAH

    1821185118811911194119712001

    0 100 200 300

    FLUORANTHENE

    1821185118811911194119712001

    0 10 20 30 40

    BENZ(a)ANTRACENE

    1821185118811911194119712001

    0 100 200 300

    CHRYSENE+TRIPHENYLENE

    1821185118811911194119712001

    0 10 20 30 40 50 60

    BENZO(a)PYRENE

    1821185118811911194119712001

    0 50 100 150 200

    BENZO(e)PYRENE

    1821185118811911194119712001

    0 1 2 3 4

    RETENE

    1821185118811911194119712001

    0 40 80 120

    PERYLENE

    1821185118811911194119712001

    0 40 80 120

    PERYLENE1821185118811911194119712001

    0 20 40 60 80

    PERYLENE

    1821185118811911194119712001

    0 2000 4000 6000

    PERYLENE

    Fig. 4. Time scales of the concentrations of total pyrolytic PAH and selected parent PAH determined from the sediment cores analysed in the

    Pyrenees and the Tatra mountains. PAH units in ng/g.

  • 22 J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    dominance of terrigenous markers among the distribu-tions of hydrocarbons and alcohols/sterols (data notreported here), are likely to be related to higher plantresidues.

    In contrast, no diagenetic formation of perylene isobserved in the downcore soil PAH mixtures (Figs. 2and 3) where this hydrocarbon is always a minorcomponent. Since most terrigenous inputs probablyoriginate from the local grassland vegetation the dif-ference from the sediment composition is probablyrelated to the lack of anoxic conditions in the soils.

    An enrichment in the relative concentration ofphenanthrene is observed when considering the PAHdowncore distributions in the soils (Figs. 2 and 3).However, this enrichment is only relative to the con-centration of the other PAH. The increase in absoluteconcentration is small. A net production of phenan-threne after sedimentation is therefore unclear. Thishydrocarbon is the end member product in the trans-formation of many diterpenoids following aromatiza-tion pathways (Simoneit, 1986; Simoneit et al., 1986).

    Retene may be produced during wood combustion(Ramdahl, 1983) or diagenesis (Simoneit, 1977; La-Flamme and Hites, 1978; Wakeham et al., 1980b). In

    contrast, benzo(b)naphtho[2,1-d]thiophene is a specificmarker of coal combustion (Fernández et al., 1996).Compilation of the retene/(reteneC benzo(b)naphtho[2,1-d]thiophene) ratio affords therefore a standardizedindex for comparison of the downcore variation ofretene vs the major pyrolytic inputs (Fig. 5). This indexmay be compared to the changes in 1,7-dimethylphe-nanthrene vs 2,6-dimethylphenanthrene which has alsobeen proposed as a marker of wood to fossil fuelcombustion (Benner et al., 1995) as shown in studies onlake Mystic and Boston harbor (Gustafsson et al., 1997).This index has been calculated for the soils and sedi-ments of the high mountain lakes considered for studyand compared to the retene index and total PAH(Fig. 5).

    The 1,7-dimethylphenanthrene/(1,7-dimethylphenan-threneC 2,6-dimethylphenanthrene) exhibits similarvalues and a rather constant downcore profile in bothRedon and Tatra sediments and soils. In contrast, theretene/(reteneCbenzo(b)naphtho[2,1-d]thiophene) indexincreases downcore in the sediments of both lakes(Fig. 5). This increase is also observed in Redon soils butnot in the Tatra soils. The sedimentary downcoreincrease of the retene/(reteneC benzo(b)naphtho[2,1-d]

    LAKE REDON (SOILS)

    0

    100

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    500

    600

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    0 2 4 6 8 10DEPTH (cm)

    )g

    /g

    n(

    H

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    or

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    00.10.20.30.40.50.60.70.80.91

    so

    it

    ar

    H

    AP

    Pyrolytic PAH

    Ret/(Ret+BNT)

    1,7-/(1,7- + 2,6)DMPhe

    LAKE REDON (SEDIMENTS)

    0

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    0 2 4 6 8 10DEPTH (cm)

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    Ret/(Ret+BNT)

    1,7-/(1,7- + 2,6)DMPhe

    LADOVE (SOILS)

    0

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    1,7-/(1,7- + 2,6)DMPhe

    LADOVE (SEDIMENTS)

    0

    2000

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    0 2 4 6 8 10DEPTH (cm)

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    so

    it

    ar

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    Pyrolytic PAH

    Ret/(Ret+BNT)

    1,7-/(1,7- + 2,6)DMPhe

    Fig. 5. Downcore distributions of pyrolytic PAH and the indices retene/(reteneC benzo(b)naphtho[2,1-d]thiophene) and 1,7-dimethylphenanthrene/(1,7-dimethylphenanthreneC 2,6-dimethylphenanthrene) in the soils and sediments from Redon and Ladove lakes.

  • 23J.O. Grimalt et al. / Environmental Pollution 131 (2004) 13e24

    thiophene) index and the nearly constant ratio of the1,7-dimethylphenanthrene/(1,7-dimethylphenanthreneC2,6-dimethylphenanthrene) sediment suggest that thepresence of retene in the deeper sediments is due todiagenetic processes. Thus, in these high mountain envi-ronments it cannot be taken as a wood combustionmarker.

    4. Conclusions

    In high mountain areas there is a better parallelismbetween the PAH composition in long-range trans-ported aerosol mixtures and top soil sections than in toplake sediment layers. This higher agreement is observedwhen comparing diagnostic ratios such as indeno[1,2,3-cd]pyrene/(indeno[1,2,3-cd]pyreneC benzo[ghi]perylene)but also ratios involving photochemically labile com-pounds such as benz[a]anthracene/(benz[a]anthraceneCchryseneC triphenylene), benzo[a]pyrene/(benzo[a]pyreneC benzo[e]pyrene) and methylphenanthrenes/(methylphenanthrenesC phenanthrene). In all cases,labile PAH are found in higher relative concentrationin soils and the corresponding ratios are closer to thosefound in the aerosols than in the lake sediments. Thecontrast between these two environmental compart-ments points to significant degradation of labile PAHduring water column transport from atmosphere tounderlying sediments in high mountain lakes.

    In contrast, at deeper core sections, higher relativeproportion is found of the more labile PAH in sedimentsthan soils. This is observed for the relative content ofbenz[a]anthracene to chryseneC triphenylene, benzo[a]pyrene to benzo[e]pyrene) and methylphenanthrenes tophenanthrene. Thus, after sedimentation, preservationof the labile PAH is better in the lake sediments than insoils from the catchment.

    The diagenetic processes in soils and sediments are alsodifferent, involving the formation of major amounts ofperylene in the later but not in the former. In soilsdowncore enrichment of phenanthrene is observedmaybeas a consequence of the extensive aromatization ofditerpenoid compounds. In this respect, examination ofthe retene/(reteneC benzo(b)naphtho[2,1-d]thiophene)and the 1,7-dimethylphenanthrene/(1,7-dimethylphe-nanthreneC 2,6-dimethylphenanthrene) ratios in sedi-ments and soils indicates a diagenetic origin for thisditerpenoid.

    Acknowledgements

    Financial support from EMERGE and EUROLIM-PACS Projects is acknowledged. Barend L. van Droogethanks Autonomous University of Catalonia. RoserChaler and Dori Fanjul (Department of Environmental

    Chemistry, CSIC) are acknowledged for technicalassistance in instrumental analysis. Evzen Stuchlik,Simon Patrick, Jordi Catalan and Lluis Camarero arethanked for the sediment and soil cores sampling.

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    Polycyclic aromatic hydrocarbon composition in soils and sediments of high altitude lakesIntroductionMaterials and methodsMaterialsSamplingAnalysisSample extractionInstrumental analysisQuantificationQuality controlTotal organic carbonRadiometric dating

    Results and discussionLake featuresPAH distributionsRegular differences in soil and sediment PAH compositionDowncore sedimentary PAHDiagenetic formation of PAH

    ConclusionsAcknowledgementsReferences

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Polycyclic aromatic hydrocarbon composition in soils and sediments of high altitude lakes Joan O. Grimalt a, * , Barend L. van Drooge a , Alejandra Ribes a , Pilar Ferna´ndez a , Peter Appleby b a Department of Environmental Chemistry, Institute of Chemical and Environmental Research (ICER-CSIC), Jordi Girona 18-26, 08034 Barcelona, Catalonia, Spain b Department of Mathematical Sciences, University of Liverpool, P.O. Box 147, Liverpool L69 3BX, UK Received 4 September 2003; accepted 9 February 2004 ‘‘Capsule’’: The concentrations of polycyclic hydrocarbons in soils are more strongly correlated with deposition rate than the concentrations in sediments. Abstract Polycyclic aromatic hydrocarbons (PAH) in lake sediments and nearby soils of two European high mountain regions, Pyrenees and Tatra, have been studied. Similar mixtures of parent PAH were observed in all cases, indicating predominance of airborne transported combustion products. Nevertheless, the composition of these atmospherically long-range transported PAH was better preserved in the superficial layers of soils than sediments. This difference points to significant PAH degradation process, e.g. during lake water column transport, before accumulation in the latter. Post-depositional transformation was also different in both types of environmental compartments. Thus, lake sediments exhibit higher preservation of the more labile PAH involving lower degree of post-depositional oxidation. However, they also show the formation of major amounts of perylene by diagenetic transformation in the deep sections. This compound is not formed in soils where downcore enrichments of phenanthrene are observed, probably as a consequence of diagenetic aromatization of diterpenoids. Ó 2004 Elsevier Ltd. All rights reserved. Keywords: Polycyclic aromatic hydrocarbons; High maintain areas; Soil pollution; Lake pollution; Long-range transported pollutants; Combustion pollution 1. Introduction PAH in the environment deserve increasing attention for their widespread occurrence and mutagenic, carci- nogenic and teratogenic effects (Freitag et al., 1985). They may be generated from organic matter diagenesis and anthropogenic processes (Simoneit, 1977; La- Flamme and Hites, 1978; Wakeham et al., 1980a,b). However, the anthropogenic contribution usually out- weighs the inputs from other sources and is responsible for their general increase over the last 100 yr (Hites et al., 1977; Ferna´ndez et al., 2000). Depending on their physico-chemical properties, atmospheric PAH are distributed between the gas and particulate phases, mainly in association with small particles ( !1 mm) (Aceves and Grimalt, 1993; Masclet et al., 1988; Allen et al., 1996; Ribes et al., 2003). They are transported through the atmosphere to remote sites giving rise to a general background level in soils (Hartmann, 1996; Wilcke and Zech, 1997; Wild and Jones, 1995; Vogt et al., 1987; Berteigne et al., 1988; Jones et al., 1989a,b; Guggenberg et al., 1996; Wilcke et al., 1996) and lake sediments (LaFlamme and Hites, 1978; Gschwend and Hites, 1981; Atlas et al., 1981; Simcik et al., 1996; Ferna´ ndez et al., 1996, 1999, 2000) where they accumulate due to their high stability and small mobility as a consequence of their low water solubility. Soils and lake sediments are therefore good environmental * Corresponding author. Tel.: C34-93-4006122; fax: C34-93- 2045904. E-mail address: [email protected] (J.O. Grimalt). Environmental Pollution 131 (2004) 13e24 www.elsevier.com/locate/envpol 0269-7491/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.envpol.2004.02.024
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