The use of mosses and pine needles to detect persistent organicpollutants at local and regional scales

I. Holoubek a,*, P. KorÏ õ nekb, Z. SÏ eda a, E. Schneiderova c,I. Holoubkova c,d, A. Pacl d, J. TrÏ õ ska e, P. Cudlõ n e,

J. CÏ a slavsky f

aResearch Centre for Environmental Chemistry and Ecotoxicology (RECETOX), Masaryk University,

VeslarÏska 230B, 637 00 Brno, Czech RepublicbHygienic Survey, Cornovova 68, 618 00 Brno, Czech RepubliccTOCOEN Ltd., VeslarÏska 230B, 637 00 Brno, Czech Republic

dObservatory KosÏetice, 394 22 KosÏetice, Czech RepubliceInstitute of Landscape Ecology, Academy of Science, CÏeske BudeÏjovice, Czech Republic

fInstitute of Analytical Chemistry, Academy of Science, Brno, Czech Republic

Received 22 February 1999; accepted 13 September 1999

``Capsule'': Moss and pine needles were found to `sample' and record spatial and temporal di�erences in a mixture ofPAHs in air.

Abstract

Polycyclic aromatic hydrocarbons (PAHs) were analysed in mosses (Hypnum cupressiforme) and pine needles (Pinus sylvestris)collected in the Czech Republic between 1988±94 at a regional background site in KosÏ etice, south Bohemia (1988±94) and two

industrial sources. One industrial site (sampled 1989±91) in middle Moravia, was near a factory producing PAHs, carbon black andphthalates, the other (sampled 1991±93) near a coal and gas fuel production plant in western Bohemia. Selected chlorinated pesti-cides and polychlorinated biphenyl congeners were also analysed in samples at the regional background site. This study clearlyshows that vegetation sampling can be used to show spatial di�erences in the atmospheric burden of a range of persistent organic

pollutants with di�erences in the mixtures of compounds re¯ecting di�erences in their regional or local use/atmospheric emission.# 2000 Elsevier Science Ltd. All rights reserved.

1. Introduction

Many recent studies have used vegetation whichbioaccumulates organic pollutants for monitoring stu-dies (Larsen et al., 1985; Reischl et al., 1989; Moser etal., 1991; Kylin, 1994; Simonich and Hites, 1995). Thesepapers describe the mechanisms of uptake by vegeta-tion, the use of vegetation to indicate contamination levels,and the importance of vegetation as a pollutant sink.The mechanism of vegetation uptake of organic pollu-

tants is governed by the chemical and physical proper-ties of pollutant (such as their molecular weights, aque-ous solubilities, and vapour pressures), environmentalconditions (the atmospheric temperature), and the plant

species and structure (Simonich and Hites, 1995). Vege-tation can be used to qualitatively indicate organic pol-lutant atmospheric contamination levels as long as themechanism of accumulation is considered. Vegetation hasbeen used to identify point sources of pollutants and todetermine regional and global contamination patterns.There are several pathways through which organic

pollutants enter vegetation. The pollutant may enterthe plant by partitioning from contaminated soil to theroots and be translocated in the plant by the xylem.Organic pollutants may also enter vegetation from theatmosphere by gas- and particle-phase deposition ontothe waxy cuticle of the leaves or by uptake through thestomata and be translocated by the phloem.These pathways are a function of: (1) the chemical

and physical properties of the pollutant, such as itslipophilicity, water solubility, vapour pressure (whichcontrols the vapour±particle partitioning), and Henry's

0269-7491/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.

PI I : S0269-7491(99 )00260-2

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www.elsevier.com/locate/envpol

* Corresponding author. Tel.: +420-5-43-21-03-95; fax: +420-5-

43-32-12-95.

E-mail address: holoubek@chemi.muni.cz (I. Holoubek).

law constant; (2) environmental conditions, such asambient temperature and the organic content of the soil;and (3) the plant species, which controls the surfacearea and lipids available for accumulation.Many researchers have used pollutant concentrations

in vegetation to qualitatively indicate atmospheric con-tamination levels. Vegetation integrates contaminationover time, and vegetation samples are much easier tocollect than air samples, especially in remote locations.Vegetation has been used to identify point sources oforganic pollutants, to determine regional contaminationwithin cities, countries, and continents, and to deter-mine the global contamination of organic pollutants(Simonich and Hites, 1995).Many studies have monitored the atmospheric

deposition of both heavy metals and organic pollutantsby epiphytic mosses (Oehme et al., 1985). Mosses do nothave a root system, so that the uptake of nutritive sub-stances and pollutants therefore occurs exclusively viathe atmosphere. The annual rate of growth is easilydetectable, which allows the determination of air pollu-tants collected during one growth period.Vegetation has been used to indicate ubiquitous pol-

lutant contamination levels. In order to determine thegeneral contamination level of cities, countries, andcontinents, many samples from a variety of locationsare required in order to minimize the e�ect of pointsources and overcome the inherent variability of sam-ples from the same site.This paper describes a study in which moss and pine

needle samples were collected from the ®eld sites ofProject TOCOEN (Holoubek et al., 1990a)Ðfrom thesurroundings of two industrial factories [The Coal andGas Fuel Company VrÏ esova , in the period 1991±93,TOCOEN study area No. 10 (Fig. 1); and DEZAValasÏ ske MezirÏ õ cÏ õ , 1990±91, TOCOEN study area No.5] and from a background site at the KosÏ etice observa-tory (1988 up to date, TOCOEN study area No. 3).

1.1. Sample locations

The KosÏ etice observatory of the Czech Hydro-meteorological Institute was established as a regional

station of the integrated background monitoring net-work of the United Nations Environmental Programme(UNEP) project Global Environmental MonitoringSystem (GEMS). The observations were launched at theend of the 1970s; the building of the observatory wascompleted in 1988 (Va nÏ a et al., 1997). The monitoringarea comprises the Anensky Brook basin and the stationitself, situated outside this basin.The climatic classi®cation of the area where the

observatory is located (ZÏ elivska Hills) comes undermoderately warm and moderately humid upland zones.The basic characteristics for the period 1961±90 were:mean annual temperature, 7.1�C; annual precipitationtotal, 621 mm; number of snow-cover days, 60±100 peryear; sunshine, 1800 h year.This part of project TOCOEN is focused on the

determination of polycyclic aromatic hydrocarbons(PAHs), organochlorine pesticides (OCPs) and poly-chlorinated biphenyls (PCBs) in the air samples (AÐonce in a month), rain water samples (RWÐeveryevent), surface waters, (W), sediments (SED), soils (S),terrestrial biota [earthworms (E), mosses (N) andneedles (N)Ðonce in a year]. The sampling periodstarted in the fall of 1988.The major local source of PAHs is the Corporation

DEZA ValasÏ ske MezirÏ õ cÏ õ (Fig. 1, No. 5) (Holoubek etal., 1991). Crude tar and benzene are processed by themanufacturing plant of DEZA and a rich assortment ofproducts results. Crude benzene processing yields purebenzene, pure and varnish toluene, xylene, and solventnaphtha. Tar distillation produces road tar for roadsurfaces and tar being used as a binding agent in thebuilding industry. A large number of fractions aresemi-®nished products which are transferred from thetar distillation department to another manufactur-ing department, e.g. to the department producingpure anthracene. Another manufacturing department,which produces technical naphthalene supplies thephthalic anhydride manufacture with initial material.Phthalic anhydride is a parent material for dioctylphthalate which is used as a plasticizer. Oil furnaceblack is also produced in signi®cant quantities. Thirty-seven sampling sites were established for the collectionof air, sediments, soils, earthworms, needles, mosses andaquatic biota. The measurements were started in 1989.The Coal and Gas Fuel Company VrÏ esova is situated

in the Sokolov coal basin between the cities KarlovyVary and Sokolov (Fig. 1, No. 10). This company car-ries out lignite mining in this part of the coal basin andproduces briquettes, city gas, power, heat, tar, crudebenzene, phenol concentrate, liquid ammonia and otherproducts. The company is an important producer offuels and power, which enables it to contribute toimprovements of the social and economic life of theregion. On the other hand, the company has negativee�ects, the worst being ecological, resulting from theFig. 1. Model areas of Project TOCOEN in former CSFR.

284 I. Holoubek et al. / Environmental Pollution 109 (2000) 283±292

concentration of di�erent industrial activities in a rela-tively small area. The surroundings of the companyhave been selected as study site No. 10Ða sourceof PAHs. Measurements here were started in 1991.Twenty-one sampling sites were established around thisfacility for the collection of air, sediments, soils, earth-worms, needles, mosses and aquatic biota.

1.2. Sample collection

Mosses (Hypnum cuprresiforme L. ex Hedw.) andpine needle (Pinus sylvestris L.) samples were collectedat the area of observatory KosÏ etice (®ve sampling sitesfor mosses and six for needles), in the surround-ings of DEZA ValasÏ ske MezirÏ õ cÏ õ (®ve and eight sam-pling sites), and the Coal and Gas Fuel CompanyVrÏ esova (nine and six sampling sites) (Holoubek et al.,1990b, 1991). Samples from the observatory KosÏ eticewere collected annually from the year 1988, whilesamples from the suroundings of factories were col-lected during the years 1989±91 in the case of DEZAValasÏ ske MezirÏ õ cÏ õ and during the years 1991±93 in thecase of the Coal and Gas Fuel Company VrÏ esovaÂ(annually again).The moss samples were collected on the ground out-

side the crown projection of trees. Pine needles (3 yearsold) were collected in the same way and wrapped inaluminium foil, air-dried at ambient temperature andstored in paper and sealed polyethylene bags in thedark, at room temperature until analysis. Mossesand pine needles from the observatory KosÏ etice, wereanalyzed for PAHs, PCBs and OCPs, mosses andpine needles from the suurroundings of companiesin VrÏ esova and ValasÏ ske MezirÏ õ cÏ õ , respectively, wereanalysed for PAHs only.

1.3. Chemicals

Chemical standards of PAHs, OCPs and PCBs werepurchased from Supelco Inc. All compounds were ana-lytical standards of >99% purity. All other chemicalsused were for residue analysis.

1.4. Chemical analysis

After a partial oven drying (24 h, normal tempera-ture), the samples were minced and weighed in glassextraction thimbles, and the extraction was performedwith a Soxhlet apparatus using dichloromethane (8 h).Sulphuric acid clean-up was used. Florisil columnchromatography was performed after reduction of thevolume by a rotary evaporator operated at 45�C. Flor-isil was previously dried (130�C; 4 h) and washed withacetone and n-hexane. Samples were then adsorbed onthe ¯orisil phase and eluted by n-hexane (OCPs, PCBs)and by dichloromethane (DCM) (PAHs). The volume

of the samples was reduced by rotary evaporation to5 ml and then in a stream of nitrogen to a ®nal volumeof 0.5 ml ready for chromatographic analysis.Analysis was performed by HRGC/MSD on an HP

6890 (PAHs) (column HP-5MS, 30 m�0.25 mm�0.25mm, temperature programme: 80�C/1 min, 5�C/min,280�C/10 min, detectionÐSIM mode), and HRGC-ECD HP 5880 (OCPs, PCBs) (column NB-54, 50 m�0.2mm�0.1 mm, temperature programme: 50�C/0.5 minÐ20�C/minÐ220�CÐ1.5�C/minÐ280�C/1 min). The detec-tion limit was �0.1 ng gÿ1 dry weight, assuming 10 g ofsample.

1.5. Quality assurance/quality control (QA/QC)protocol

The procedures described above have been checkedfor recoveries and reproducibility. Prior to extraction,the extraction was investigated by spiking pine needleand moss subsamples with four increasing amounts ofthe standards. For all the compounds analysed, recov-ery results were in the 80 and 98% range. Reproduci-bility was calculated on replicate analyses, giving anerror of between 2.7 and 8.3%. One analytical blankwas prepared using the same extraction and clean-upprocedure with samples for every campaign and sam-pling site. Twenty per cent of samples were extractedand analysed in duplicate. A solvent blank was analysedafter every 15 samples as a check on the response of thegas chromatography (GC). Concentration data arereported on a ng gÿ1 dry weight basis, not consideringthe speci®c lipid content of each sample.

2. Results and discussion

2.1. Regional and local observations of PAHs levels inthe Czech Republic

The mean and range of concentrations of PAHsmeasured in moss and pine needle samples at each siteare reported in Tables 1 and 2. Typical mixtures ofPAHs are shown for each sampling area in Fig. 2.The �PAHs content in mosses ranged from <0.3 to

4700 ng gÿ1 dry weight (mean value 609) in the back-ground site (TOCOEN study area 3). Concentrationswere elevated above this range at the industrial sites:229±10,222 ng gÿ1 (mean value 3060) in TOCOENstudy area 5, and <0.3±16,730 ng gÿ1 (mean value3670) in study area 10.Acenaphthene, anthracene, chrysene, and indeno[1,2,

3-c,d]pyrene dominated the PAHs burden of samplesfrom the background sampling sites. In contrast naph-thalene, ¯uorene, phenanthrene, ¯uoranthene, benzo-[a]anthracene, chrysene, benzo[b]¯uoranthene andbenzo[a]pyrene dominated near the local source in

I. Holoubek et al. / Environmental Pollution 109 (2000) 283±292 285

study area 3 and acenaphthylene, acenaphthene, benzo-[a]pyrene, indeno[1,2,3-c,d]pyrene, and benzo[g,h,i]-perylene near the local source in study area 10.The �PAHs content in pine needles ranged from

<0.3 to 18,590 ng gÿ1 dry weight with (mean value1345) at background site and from <0.3 to 16,733 nggÿ1 (mean value 5731) and from 85 to 19,251 ng gÿ1

(mean value 8325) at the two industrial sites. The mix-tures of PAHs were rather di�erent in the needlescompared to the mosses as shown in Fig. 2.

Since the exposure time for both mosses and pineneedles is practically the same, the di�erences betweentheir mixtures presumably re¯ects di�erences in therelative importance of compound capture from theatmosphere.A study of the spatial distribution and mixture of

PAHs in pine needles sampled across the UK (Tremo-lada et al., 1996) showed that phenathrene was thepredominant compound in PAH mixtures. This pre-dominance was not observed in needles from the Czech

Table 1

Means and ranges of polycyclic aromatic hydrocarbons (PAHs) (ng gÿ1) in mosses observed at background site KosÏ etice and two industrial sites

Sampling area KosÏ etice ValasÏ ske MezirÏ õ cÏ õ VrÏ esovaÂ

Number of sampling sites 5 5 9

Number of samples during whole campaign 36 15 33

Sampling period 1988±94 1989±91 1991±93

Observed compounds (ng gÿ1)Naphthalene (NAP) 24.4 129.7 109.3

<1±700 <1±1647 <1±719

Acenaphthylene (ACL) 7.8 51.9 113.9

<1±163 <1±649 <1±1311

Acenaphthene (ACE) 45.3 16.7 200.3

<1±1183 <1±93.9 <1±2048

Fluorene (FLR) 68.8 325 19.5

<1±933 <1±1555 <1±97.7

Phenanthrene (PHE) 43.3 318.5 76.4

<0.6±380 <0.6±2453 <0.6±279

Anthracene (ANT) 68.6 59.6 0.95

<0.6±2280 <0.6±377 <0.6±27

Fluoranthene (FLU) 18.9 349.6 140.7

<0.6±325 <0.6±2498 <0.6±453

Pyrene (PYR) 128.5 122.9 57.7

<0.9±525 <0.9±476 <0.9±675

Benzo[a]anthracene (BaA) 13.7 428.4 13.9

<0.9±311 <0.9±3636 <0.9±127

Chrysene (CHR) 74.6 276.3 105.4

<0.6±1190 <0.6±1833 <0.6±689

Benzo[b]¯uoranthene (BbF) 5.3 476.2 77.5

<0.6±84 <0.6±2050 <0.6±338

Benzo[k]¯uoranthene (BkF) 6 87.8 134.7

<0.6±120 9.5±281 <0.6±598

Benzo[a]pyrene (BaP) 37.9 356.1 289.5

<0.3±540 10.95±2976 <0.3±1592

Indeno[1,2,3-cd]pyrene (INP) 94.5 243.1 1350.1

<0.6±1087 <0.6±610.4 <0.6±5721

Dibenzo[a,h]anthracene (DBA) 23 50.5 468.3

<0.6±460 <0.6±333 <0.6±9653

Benzo[g,h,i]perylene (BPE) 14.5 413.4 938.2

<0.3±290 <0.3±1789 <0.3±5792

�PAHs 609.1 3056.9 3669.9

<0.3±4700 229±10,222 <0.3±16,733

286 I. Holoubek et al. / Environmental Pollution 109 (2000) 283±292

Republic. The detection of PAHs in all of the PAHsanalysed in the moss and needle samples from thoseregional background site can beÐsimilar to an examplein the UK (Tremolada et al., 1996)Ðinterpreted as evi-dence for widespread di�usive PAH contaminationthroughout the troposphere, which is supplemented insome areas by elevated inputs. Evidence for widespreaddi�usive inputs and environmental occurrence of PAHsin both countries (Czech Republic, UK) has beenpublished previously (Holoubek et al., 1990b, 1991;Tremolada et al., 1996).

Near the local sources in study areas 3 and 10, themoss and pine needle samples were collected on fourtransects, along the main wind directions. The distancebetween points on the transects was variable, depend-ing on the occurrence of mosses and needles. Fourtransects for mosses and two for pine needles wereused in the surroundings of the source in area 3 and twofor mosses and pine needle transects were used in area10. These two sampling areas have di�erent types ofPAH contamination. The source in area 3 is typicallya point source and dominant as a source of PAHs

Table 2

Means and ranges of polycyclic aromatic hydrocarbons (PAHs) (ng gÿ1) in pine needles observed at background site KosÏ etice and two industrial sites

Sampling area KosÏ etice ValasÏ ske MezirÏ õ cÏ õ VrÏ esovaÂ

Number of sampling sites 6 8 6

Number of samples during whole campaign 45 18 12

Sampling period 1988±94 1989±91 1991±93

Observed compounds (ng gÿ1)Naphthalene (NAP) 22.6 303.1 222.6

<1±640 <1±1077 <1±1104

Acenaphthylene (ACL) 699.8 415.5 3088.8

<0.5±14,070 <0.5±4019 <0.5±8359

Acenaphthene (ACE) 58.3 2291.2 723.5<0.5±730 <0.5±27,169 <0.5±8653

Fluorene (FLR) 151.4 566.8 216.8

<1±1819 <1±3025 <1±1305

Phenanthrene (PHE) 29.6 478.9 1194.8<0.3±1060 <0.3±3043 <0.3±3978

Anthracene (ANT) 60.4 307.7 413.8

<0.3±700 <0.3±2449 <0.3±3407

Fluoranthene (FLU) 24.7 364.3 261.7<0.3±280 <0.3±2046 <0.3±798

Pyrene (PYR) 15 113.9 95.1

<0.6±220 <0.6±309 <0.6±635

Benzo[a]anthracene (BaA) 94.3 62.1 1339.3<0.6±8380 <0.6±189 <0.6±6211

Chrysene (CHR) 39 99.6 351.6<0.6±520 <0.6±600 <0.6±2311

Benzo[b]¯uoranthene (BbF) <0.6 134.6 2<0.6±383 <0.6±24

Benzo[k]¯uoranthene (BkF) <0.6 97.8 23.5<0.6±247 <0.6±282

Benzo[a]pyrene (BaP) 132.6 478.9 208<0.3±3530 <0.3±1911 <0.3±1254

Indeno[1,2,3-cd]pyrene (INP) 17 58.4 7.1<0.6±1530 <0.6±239.6 <0.6±54

Dibenzo[a,h]anthracene (DBA) 5.1 53.7 2.2

<0.6±460 <0.6±570 <0.6±27

Benzo[g,h,i]perylene (BPE) 3.2 195.6 174.4<0.3±290 <0.3±867 <0.3±711

�PAHs 1344.6 5730.6 8325.2

<0.3±18,590 <0.3±16,733 85±19,251

I. Holoubek et al. / Environmental Pollution 109 (2000) 283±292 287

Fig. 2. The comparison of observed PAHs levels in mosses and pine needles from background site KosÏ etice and two industrial sites.

288 I. Holoubek et al. / Environmental Pollution 109 (2000) 283±292

in this area. The main contamination is close to thefactory and decreased with distance from the source.The source in area 10 is located in the very heavily pol-luted region of North Bohemia (the western part ofthe so-called Black Triangle), with many industrialsources of pollution (electric power plants, chemicalindustry, coal mining system, tra�c) and here PAHcontamination of moss and needle samples is more`di�usive'. Concentrations do not decrease with dis-tance from the observed source up to a distance of15 km.

2.2. Regional observations of OCPs and PCBs levels inthe Czech Republic

Table 3 reports means and ranges of Cl-PESTsand PCBs in mosses and pine needles from the back-ground area. The hexachlorobiphenyl (HCB) content inmosses from the background area ranged from <0.1to 18 ng gÿ1 (mean value 1.6) and from <0.1 to 6 nggÿ1 (mean value 2.63) in the needles. In the case of g-hexachlorocyclohexane (HCH) in mosses from thesesampling sites, the range was from <0.1 to 5.9 ng gÿ1,

with a mean value of 1.28 ng gÿ1, and in the case ofneedles ranged from <0.1 to 9.2 with a mean value 1.98ng gÿ1 dry weight. DDT and its metabolite DDE weredetected only in the moss samples and ranged from<0.1 to 6.8 ng gÿ1 (mean=1.14) and from <0.1 to 0.4ng gÿ1 (mean=0.15) (DDE), respectively.The selected PCB congeners (28, 52, 101) were detec-

ted in moss samples in the range of <0.1 to 0.6; 0.3 and0.2 ng gÿ1 dry weight, respectively, with mean values of0.17; 0.18 and 0.09 ng gÿ1 dry weight.A series of papers by Kylin and co-workers (Eriksson

et al., 1989; Jensen et al., 1992; Kylin et al., 1994;Strachan et al., 1994) has outlined the use of Scots pine(P. sylvestris) needles to determine the regional con-tamination of organochlorines in Europe. Jensen etal. (1992) collected pine needles from France, Switzer-land, Germany, Denmark, Poland, Czechoslovakia,Sweden, and Norway in 1986 and analysed them forchlorinated pesticides and PCBs. They tracked elevatedDDT concentrations in needles to the use of DDT in theformer East Germany, while most HCHs, PCBs, andHCB were ubiquitous throughout Europe. However,the concentrations of pentachlorophenol were elevatedin needles from Sweden, and lindane was elevated insamples from southern France.These researchers collected needles again in 1989 from

some of the same sites and analysed them for the samecompounds (excluding PCBs) (Strachan et al., 1994).The results were similar to the previous study. Lindaneconcentrations in needles decreased slightly from thesouth to north, while the concentrations of a-HCH andHCB were uniform throughout the sites. The ratio ofDDT to DDE decreased from south to north, and theconcentrations of PeCP in north Sweden samplesremained high. This study also showed that samplingat a consistent height within the tree is preferred, thatthere is no di�erence in needle pollutant concentra-tion of trees facing di�erent directions, and that theage of the tree does not in¯uence the needle pollutantconcentration.Calamari et al. (1994) used pine needles to determine

regional contamination of DDT, HCHs and HCB inEurope. Samples were collected from Italy, Holland,Austria, Czechoslovakia, Finland, and Greece. Themeasured needle organochlorine concentrations werecompared to previous studies in other European coun-tries. These authors suggested that the organochlorinedistribution pattern, or `®ngerprint', in pine needles froma given country is dependent on use of the compounds inthat country and on its socio-economic conditions.Fig. 3 shows the organochlorine insecticide concentra-

tions in needles from some of the countries investigatedby Calamari et al. (1994) compared to the backgroundobservatory KosÏ etice. There is a wide range in organo-chlorine concentrations among the countries. The ®gureshows that parts of former Czechoslovakia (southwest

Table 3

Means and ranges values of OCPs and polychlorinated biphenyls

(PCBs) (ng gÿ1) in mosses and pine needles observed in various

sampling sites from the background area (sampling period 1988±94)

Sampling area Mosses Pine needles

Number of sampling sites 5 6

Number of samples during

whole campaign

36 45

Sampling period 1988±94 1988±94

Observed compounds (ng gÿ1)a-HCH 1.07 0.22

<0.1±3.8 <0.1±1.4

HCB 1.6 2.63

<0.1±18 <0.1±6

b-HCH <0.1 <0.1

g-HCH 1.28 1.98

<0.1±5.9 <0.1±9.2

d-HCH <0.3 <0.3

E-HCH <0.3 <0.3

PCB 28 0.17 <0.1

<0.1±0.6

PCB 52 0.18 <0.1

<0.1±0.3

PCB 101 0.09 <0.1

<0.07±0.2

p,p0-DDE 0.15 <0.1

<0.1±0.4

p,p0-DDT 1.14 <0.1

<0.1±6.8

I. Holoubek et al. / Environmental Pollution 109 (2000) 283±292 289

Fig. 3. The comparison of levels of OCPs from Czech regional background observatory and various European sites.

290 I. Holoubek et al. / Environmental Pollution 109 (2000) 283±292

Slovakia) were the most contaminated of those sampled,while the KosÏ etice background region (Czech Republic)and Finland were much less contaminated.The Czech and Greece ®ngerprints were not char-

acterised by any particular insecticide, while Finlandwas relatively high on a-HCH and Italy was char-acterised by high p,p0-DDT.Although most of these studies analysed a relatively

small number of vegetation samples collected from alimited number of sampling sites, they show that vege-tation can be used as an indicator of regional con-tamination levels.Table 4 compares recently published data with data

from this current study for the Czech Republic.

3. Conclusions

As Lead and co-workers clearly described (Lead et al.,1996), the various plant species are ideal biomonitors.They play an important role in the global cycling ofpersistent organic pollutants (POPs) since they coverover 80% of the Earth's land surface, the surface area ofplants is generally much greater than the area of theground they cover, and the vegetation has a high lipidfraction which is likely to accumulate lipophilic persis-tent organic compounds.The collection of mosses and pine needles for deter-

mination of airborne POPs is a suitable technique formonitoring these compounds. Mosses are suitablefor the above three reasons and also because theydepend entirely on the atmosphere for delivery ofnutrients and lack both cuticle and internal transportmechanisms. The waxy surface of the pine needles trapsgaseous airborne pollutants and also traps particulatesand, thus, pollutants associated to the particles to acertain extent (Kylin et al., 1994).

Epiphytic mosses and conifer needles have been usedfor monitoring both local and regional distribution ofPOPs. They can be particularly useful for identifyingunknown point sources of pollutants as shown recentlyby Hermanson and Hites (1990) for the determinationof historical PCB contamination (Wagrowski and Hites,1997) and for PCDD/F contamination from penta-chlorophenol wood-preserving factories (Safe et al.,1992). All these studies indicate that vegetation can beused to pinpoint local pollutant sources.The results of this study can be interpreted in terms of

regional use, and the collection of mosses and pineneedles can be readily and repeatedly done from treesin a given location (Strachan et al., 1994). In the caseof PAHs, mosses re¯ect more the di�erences betweenbackground locality and polluted areas, suggestive ofcontinuing/ongoing sources of these compounds.

Acknowledgements

The research was supported by funds from the CzechMinistry of the Environment (Project VaV 340/2/96),Czech Hydrometeorological Institute, DEZA ValasÏ skeÂMezirÏ õ cÏ õ , Coal and Gas Fuel Company VrÏ esova , GrantAgency CR (project No. 511/95/10/60), and ProjectTOCOEN and was performed as a part of researchprogramme of European Scienti®c Foundation (ESF)Research network on Persistent, Bioaccumulative andToxic Chemicals.

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Table 4

The comparison of concentrations (ng gÿ1) of selected chlorinated

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of the needlesa±d

Finland Germany UK Czech Republic

a-HCH 0.463±1.929 <0.1±1.4

g-HCH 0.401±1.707 <0.1±9.2

HCB 0.213±0.731 <0.1±6

PCB 28 0.48±27.03 0.21±25.56 <0.1

PCB 52 0.46±13.05 0.42±5.73 <0.1

PCB 101 0.47±12.05 2.17±5.38 <0.1

�PAHs 19±3090 <0.3±19,251

a The vicinity of metal reclamation plant (Sinkkonen et al., 1992).b The vicinity of the Ruhr industrial area (Strachan et al., 1994).c South and Central Sweden (Strachan et al., 1994).d Study of spatial distribution of PAHs in UK atmosphere using

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