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The German heavy metal survey by means of mosses
TheScience of theTotal Environment I82 (1996)159-168
ELSEVIER
The German heavy metal survey by means of mosses B. MarkerPa, U. Herpinb, U. Siewers’, J. Berlekampb, H. Liethb, aIntematianal Graduate School (MI). Markt 23, D-02763 Zittau, FRG bInstitute for Environmental System Research, University of Osnabriick, Artilleriestrasse 34, D-4*76 Osnabriick. FRG cFederal Institute for Geosciences and Natural Resources, Stilleweg 2, D-30655 Hanrwver, FRG
Received 5 July 1995;accepted 2 November1995
Thisis the first attempt to determinepollution with metalsthroughoutthe FederalRepublicof Germanyby analysing mosssamples.Samplesof Pleurozium schreberi, Scleropodium ptuum, Hypnum cupessifotme and Hylocomitun splen&ns werecollectedat 593sitesand analysedby ICP-AES andAAS for the elements As, Cd, Cr, Cu, Fe, Ni, Pb, V andZn. Citrusleavesand pineneedleswereusedasreferencematerialsto ensurethe quality of the results.In many cases it waspossibleto trace the areasaffectedby known sourcesof heavy-metalemissions in addition to isolatedlocal increases in the values.The mossmonitoringprogrammeshowedup the highly industrializedand urbanlocationssuch asthe Ruhr, partsof the Garland and Baden-Wiitttembergand largeareasof easternGermany.Lowerlevelsof many elements werefound in wide stretchesof Lower Saxonyand Bavaria.The resultslargely reflect the pollution patterns found in theseareas.On the other hand,expectedcorrelationsbetweenthe effectsof traffic (e.g.Pb) andconcentrations in mosscould not bedemonstratedwith certainty. The elementdata yieldedby this projectare Germany’scontribution to the Europeanproject ‘AtmosphericHeavy Metal Depositionin Europe- Estimationsbasedon MossAnalysis’. Keywords: Biomonitoring;Heavy metals;Germany; Mosses;Survey
1. Introductiorl
The insidious accumulation of heavy metals over large areas and long periods, resulting in slow damage to living organisms, necessitates careful monitoringof the input, movements and effects of such pollutants. In recent years there has been a search for ways of determining heavy-metal deposition. The aim is to identify alternatives to conventional investiga* Corresponding author.
tion methods, especially in respect of precipitation,
as these are often very costly, fraught with analytical diff&&ies, and complicated by the inhomogeneous nature of precipitation. The new methods were to be simple, integral, representative and at the same time inexpensive (Fauth et al., 1985; Siewers and Roostai, 1990; Kuick et al., 1993; Bloemen et al., 1995). As the biologically effective results of pollution can only be determined by carrying out measurements on the organisms themselves, the most suitable indicator organisms are plants. Used as
0048-9697LW§15.00 0 1996ElsevierScience B.V. AI1rightsreserved SSDI 0048-9697195~05028-7
160
B. Markert et al. /The Science of the Total Environment 182 (19%) 159-168
‘bioindicators’, these plants show the effects of air pollution through reactions such as changes in population dynamics, development of certain damage symptoms and/or the accumulation of pollutant substances (Amdt et al., 1987; Bargagli, 1993; Djingova and Kuleff, 1993; Garty, 1993; Markert, 1993 and 1994b; Wittig, 1993). In the late 1960s the Swedish scientists Ake Rtlhling and Germund Tyler used mosses for monitoring the presence of heavy metals in the environment (Rtlhling and Tyler, 1968, 1970). They found that in particular Hylocomium splendens and Pleurozium schreberi are excellent ‘catch organisms’ for wet and dry depositions of heavy metals; in other words, certain mosses can be used as indicators of heavy-metal pollution. Since then, use of the mosses in this way for environmental monitoring has been systematically extended (Goodmann and Roberts, 1971; Ross, 1990, Steinnes et al., 1992; Brtining and Kreeb, 1993; Markert and Weckert, 1993, 1994; Steinnes, 1993; Siebert et al., 1995; Wolterbeek et al., 1995). The great majority of moss species were found to have the special advantage that they take the nutrients they require almost exclusively from the atmosphere, as they have not developed a real root system or water-conductive tissue (ectohydrous mosses). Heavy-metal uptake therefore takes place through the surface of the plants. Only in a few mosses such as the Polytrichum species the uptake of water and thus of heavy metals is assisted by an internal transpiration stream (endohydrous mosses). In the Federal Republic of Germany a research programme coordinated jointly by the Federal Government and the Lander (states) was started in 1990 on the lines of the monitoring progamme of the Scandinavian countries to determine the level of pollution caused by deposition of heavy metals and arsenic with the aid of moss analyses. The research project has the following objectives: (1) To establish and test a nationwide measurement network, taking the guidelines of the Scandinavian moss monitoring programme into consideration (2) To determine the regional extent of pollution with specific metals
(3) To identify problem areas and local sources of emissions (4) To establish a data base for comparative repeat studies at intervals of five years (5) To present the measurements in the form of maps. The present paper provides a brief summary of the results. Detailed results are to be found in the National Report (Herpin et al., 1994), which constitutes Germany’s contribution to the European project ‘Atmospheric Heavy Metal Deposition in Europe - Estimations based on Moss Analysis’. This again is part of the ‘European Monitoring and Evaluation Programme’ (EMEP: cooperative programme for monitoring and evaluation of the long-range transmission of air pollutants in Europe), (Sloof and Wolterbeek, 1991; SchmidtGrob et al., 1993; Rtihling, 1994). 2. Sampling, sample preparation and analytical performance Mosses were collected from 473 sites in West Germany and the southern parts of what used to be the GDR (East Germany) from September to November 1991. Normally only Pleurozium schreberi and Hylocomium splendenswere collected, but in the absence of both species Scleropodiumpurum or Hypmun cupressiformewas taken instead. In addition, 112 samples were taken from the northern parts of the former GDR in 1990. Following the sampling system of the Scandinavian team, 5-10 subsamples from each site (50 x 50 m) were taken on a random basis and finally mixed to make up a total sample. Only the upper three segments of Hylocomium splendensand the green or greenish-brown parts of Pleurozium schreberi, Scleropodium purum and Hypnum cupressiforme were collected. The unwashed samples were dried at 40°C and homogenized in an agate mill. The samples were digested with HNOs under pressure in closed quartz vessels and diluted with bidistilled water to make 40 ml. The concentrations were measured by AAS and ICP/AES. The quality of the results was ensured by measurement against the standard reference materials ‘citrus leaves NIST 1572’ and ‘pine
B. Markert et al. / Tke Science of the Total Environment 182 (1994) 159-168
needles NIST 1575’ (Markert, 1994a; Marker? et al., 1994). The heavy-metal levels were shown in the form of coloured contour maps using the coordinates of the sampling points (Figs. l-9).
161
lower than those of south-east Germany were measured in some parts of the Ruhr, the RhineMainRhine-Neckar area and north Germany. The As values of all the samples analysed range from 0.08 &g to 15.9 kg/g, the median being 0.28 pg/g.
3. Results ad discussion 3.1. Arsenic (Fig. 1)
The highest levels of As were found in the southem parts of east Germany close to the border with the Czech Republic, where there is a high level of industrialization in both states. In this region there is a large number of coal-fired power stations without proper filters, and also a chemical industry. A further important factor is the burning of coal in private homes in these densely populated urban areas, and this is a good indicator for the well-known high arsenic content of the brown coal of the Czech Republic and south-east Germany. Moreover, the high levels of arsenic near Freiberg and Aue can be explained by the existence of Ni smelters and a non-ferrous metal industry. Levels that were elevated, but nevertheless significantly
3.2. Cadmium (Fig. 2) Large-scale elevated cadmium levels were found in the western part of Germany (Ruhr), where there are Zn, Cu and Fe smelters, oil refineries and a chemical industry. High cadmium concentrations were also found around Stuttgart, which is a highly industrialized area, in the Han mountains where there is a long tradition of ore mining, and in the Freiberg/Aue region which is affected by the non-ferrous metal industry. Low background levels of cadmium were found in Lower Saxony and Bavaria. All cadmium values in this investigation were between 0.13 ccg/gto 0.87 c(g/g, with a median of 0.31 c(g/g. 3.3. Chromium (Fig. 3)
The distribution
Fig. 1. Contour map for the element As.
pattern for Cr shows areas with
162
B. Markert et al, /The Science of the Total Environment 182 (19%) 159-168
Cd Ipg/gl I a E3 I
c 0.2 0.3 0.4 0.6
:
0.6 0.7 - 0.7 0.6
:
0.9 > - 0.9
_ -
0.2 0.3 0.4 0.5 0.6
--I
0
60
loo
160
2oobn
Fig. 2. Contour map for the element Cd.
:
1.0 1.0< - 2.0
I
2.0 - 3.0
:
4.0 3.0 *- 4.0 6.0
:
6.0 -_ 6.0 7.0
:
7.0 > - 9.0 8.0
-
0
Fig. 3. Contour map for the element Cr.
1
50
100160200km
B. Markert et al. /The Science of the Total Environment 182 (19%) 159-W
cu [p&I/g1 <6
I
60 6 - 10 10 _ 12 12 - 14
: I I
14 16 - 16 16 - 20 > 20
Fig. 4. Contour map for the element Cu.
Ff? [j&l < 500 I I
n
500-1000 lwo-1500 1600-zoo0 2ooo-26ccl
I zfioo-3ooo 13orso-3600 :
3Wi7-4000 >4000
-
0
Fig. 5. Contour map for the element Fe.
c
60
loo
2
160
200 km
163
164
B. Markert et al. / Tke Science of the Total Environment 182 (19%) 159-168
elevated levels in the Ruhr and Saarland, where there are important metal industries, and in all parts of eastern Germany, especially in the Lausitz region. The highest levels were found in Brandenburg (steel production) and near Stralsund. Beside various industries and coal-fired power stations, the burning of coal in private households may be responsible for the elevated Cr levels. In particular fly ashes from combustion processes seem to irdluence Cr concentrations. Low concentrations of Cr were found in the south and north of Germany. All Cr values in the analysis were between 0.5 &g to 11.8 &g, the median being 1.8 fig/g. 3.4. Copper (Fig. 4)
The distribution of Cu identifies a number of emission sources all over Germany, characterized by many well-known local sources. Examples are the copper smelters in the north of the Ruhr and a facility near Hamburg. Other important sources are the metal-working factories around Stuttgart. High local values were found near Bamberg and Wilrzburg. Generally speaking, the Cu levels found in the eastern parts of Germany are higher than those of the Ruhr. The Cu concentrations in Lower Saxony are low. All Cu measurements range between 4.1 &g to 25.5 &g, the median being 9.1 fig/g. 3.5. Iron (Fig. 5)
A comparison between west and east Germany reveals considerably higher levels in the southeastern parts, especially in the industrial area close to the Polish border. Important sources here include the ironworks near Eisenhiittenstadt and Riesa and the coal mining activities of the region. An elevated local value was found to the north of NurembergErlangen. Higher background levels in the Ruhr may be explained by the iron smelters in this area. Lower values were found in large parts of Bavaria, Lower Saxony and the south of BadenWtirttemberg. In general it should be noted that soil particles and fly ashes may influence the iron content of mosses. All Fe values ranged from 153 &g to 6257 j&g, with the median of 556 &g. 3.6. Nickel (Fig. 6)
The pattern of Ni distribution
is characterized
by elevated levels in the western and south-western parts of Germany, for example the Ruhr, the Rhine-Neckar region, the south-western parts of Baden-Wiirttemberg near Base1 (Switzerland), and the Saarland. In eastern Germany, high levels were found in Schwedt (refineries) and near the coast. The reason for the elevated concentrations is the importing of Nicontaining rock phosphate from Kola (CIS). In all the above areas high nickel concentrations reflect the possible influence of oil consumption, accumulations of power stations and various metal-working industries. Low concentrations were found in the northern parts of Lower Saxony and the south of Bavaria. The values range from 0.56 &g to 16.0 fig/g, with a median of 2.38 P&3* 3.7. Lead (Fig. 7)
Elevated Pb concentrations were found in the densely populated and industrialized western, south-western and eastern parts of Germany. The highest values were found near Rastatt and Freiberg, reflecting the non-ferrous metal working industry. In some cases it was not possible to detect a relationship between Pb patterns and traffic density. Nor was it possible to make definite statements on the inlluence of industry in the Frankfurt and Munich regions. The Pb values were between 5.1 pglg and 80.5 &g, the median being 12.9 pg/g. 3.8. Vanadium (Fig. 8)
The pattern of background levels of V is similar to that for the distribution of Ni and shows elevated levels in the Ruhr and large parts of eastern Germany, especially Saxony and Brandenburg. Local maxima were observed in the vicinity of Karlsruhe/Gaggenau, where there is a high density of oil refineries on both the German and French side of the border, and to the north of Nuremberg/Erlangen. High values were measured on the refinery sites near Schwedt. The high vanadium concentration in this area may be due to imports of V-enriched crude oil from the CIS. The high levels in the eastern parts of Germany may be influenced by coal burning and the considerable industrial activity along the border with Poland and the Czech Republic. Lower values were found
B. Markert et al. / The Science of the Total Environment 182 (1996) 159-168
Ni [m/g1 3
,.5;- z
I
2.26 - 3.00 3.00 - 3.76 3.75 _ 4.50
I m
4.50 5.26
:
6~oo >- 6.75 6.76
--I 0
w
_ 6.26 - 6.00
100
160
Fig. 6. Contour map for the efemc:nt 1G.
m r&31 :
100 16 20 26 30
:
: I
0
Fig. 7. Contour map for the element Pb.
-_ 10 16 - 20 - 2s - 35 30
36-40- 46 40 > 46
60
lfJo160203km
2cokm
165
B. Markert et al. /The Science of the Total Environment 182 (19%) 159-168
m
m m
< 2.0 3.0 4.0 5.0 6.0
: m
9.0 7.0 _- 9.0 > 9.0
m
2.0 _ 3.0 4.0 - 6.0 - 6.0 - 7.0
3
0
60
loo
150
wokm
Fig. 8. Contour map for the element V.
: m
40 <- 40 50 50 - 60 6070
:
70 90 - 90
m m
90 - 100 100 - 110
m
>
-
0
Fig. 9. Contour map for the element Zn.
110
-
60
’
loo
180
200 km
B. Markert
et al. /The
Science
of the Total Environment
in the south of Germany, for instance in Bavaria and Baden-Wiirttemberg. All values for vanadium were between 0.5 &g and 13.6 @g/g; the median was 2.86 &g. 3.9. Zinc (Fig. 9)
The highest large-scale levels were found in the Ruhr, where there is a considerable concentration of Zn, Cu and Fe smelting. Moreover, the pattern of Zn distribution showed increased concentrations in other densely populated and highly industrialized regions of western and south-western Germany, for example the surroundings of Stuttgart, the Rhine-MairVNeckar area and the Saarland. Elevated levels were also found in the industrialized areas of the Harz Mountains and around Berlin. Lower values were found in Bavaria, Thuringia and Lower Saxony. The highest values were measured in Senftenberg and Hoyerswerda, and these cannot be explained at the moment. In all, the Zn values ranged from 23.7 &g to 396 &g with a median of 50.4 &g. Acknowledgements We wish to thank the members of the study group ‘Bioindication and Analysis of Effects’ for their assistance during the sampling period. This is a project (UBA-FB 94125/108 02 087) founded by the Federal Environmental Agency in the Environmental Research Plan of the Federal Environment Ministry). Dr. Bau of the UBA is thanked for overall coordination of the project and Mrs. M. Braase (Buchholz, FRG) for the English translation. References Amdt, U., W. Nobel and B. Schweitzer, 1987. Bioindikatoren, Mi?@ichkeiten, Grenaen und neue Erkenntnisse, Verlag Eugen Ulmer, Stuttgart, p. 388. Bargagb, R., 1993. Plant leaves and lichens as biomonitors of natural and anthropogenic emissions of mercury. In: B. Markert (Ed.), Plants as Biomonitora&tdicators for Heavy Metals in the Terrestrial Environment, VCH Publisher, Weinheim, 1993, pp. 461-484. Bloemen, ML., B. Markert and H. Lieth, 1995. The distribution of Cd, Cu, Pb and Zn in topsoils of Gsnabrijck in relation to land use. Sci. Total Environ., 166: 137-148. Btining, F. and K.H. Kreeb, 1993. Mosses as biomonitors of
182 (1996)
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161
heavy metal contamination within urban areas, In: B. Markert (Ed.), Plants as Biomonitors/Indicators for Heavy Metals in the Terrestrial Environment. VCH Publisher, Weinheim, 1993, pp. 395-402. Djingova, R. and I. Kuleff, 1993. Monitoring of heavy metal pollution by Taraxacwn officinale. In: B. Markert (Ed.), Plants as Biomonitotindicators for Heavy Metals in the Terrestrial Environment, VCH Publisher, Weinheim, 1993, pp. 435-460. Fauth, H., R. Hindel, U. Siewers, J. Zitmer, 1985. Geochemischer Atlas Bundesrepublik Deutschland - Verteilung von Schwermetallen in W&em und Bachsedimenten, Brmdesanstalt fiir Geowissenschaften und Rohstoffe, Schweizerbart’sche Verlagsbuchhandlung (Nigele und Obermiiller), Stuttgart. Garty, J., 1993. Lichens as biomonitors for heavy metal pollution. In: B. Market? (Ed.), Plants as Biomonitors/ Indicators for Heavy Metals in the Terrestrial Environment. VCH Publisher, Weinheim, 1993, pp. 193-264. Goodmann, G.T. and T.M. Roberts, 1971. Plants and soils as indicators of metals in the air, Nature, 231: 287-292. Herpin, U., B. Marker& U. Siewers and H. Lieth, 1994. Monitoring der Schwermetallbelastung in der Bundesrepublik Deutschland mit Hilfe von Moosen. Forschungsbericht 108 02 087 im A&rag des Umwehbundesamts, Berlin, 161 S. Kuick, P., M. Blaauw, J.E. Sloof and H.Th. Wolterbeek, 1993. Application of Monte-Carlo assisted factor analysis to large sets of environmental pollution data. Atmos. Environ., 27A(13): 1975-1983. Markert, B. (Ed.), 1993. Plants as Biomonitors/Indicators for Heavy Metals in the Terrestrial Environment, VCH Publisher, Weinheim, p. 640. Markert, B. (Ed.), 1994a. Environmental Sampling for Trace Analysis. VCH Publisher, Weinheim, p. 524. Markert, B., 1994b. Biomonitoring - Quo Vadis? Z. Umweltchem. Gkotox., 6(3), 145-149. Marker& B. and V. Weckert, 1993. Tie-and-site integrated long-term biomonitoring of chemical elements by means of mosses. Toxicol. Environ. Chem., 40: 43-56. Markert, B. and V. Weckert, 1994. Higher lead concentrations in the environment of former West Germany after the fall of the ‘Berlin Wall’. Sci. Total Environ., 158: 93-96. Marker& B., U. Reus and U. Herpin, 1994. The application of TKRF in instrumental multielement analysis of plants, demonstrated with species of moss. Sci. Total Environ., 152: 213-220. Ross, H., 1990. On the use of mosses (Hylocomium splendens and Pleurozium schrebert) for estimating atmospheric trace metal deposition. Water, Air and Soil Pollution, 50: 63-76. Riihiing, A. and G. Tyler, 1968. An ecological approach to the lead problem. Botaniska Not&r, 122: 248-342. Riihling, A. and G. Tyler, 1970. Sorption and retention of heavy metals in the woodland moss Hylocomium splenah (Hedw.). Br et Sch. Oikos, 21: 92-97. Riihling, A. (Ed.), 1994. Atmospheric heavy metal deposition in Europe - estimations based on moss analysis. Nord 199419.
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S&mid-Grob, I., L. Th6ni and J. Hertz, 1993. Bestimmung de.r Deposition von Luftschadstoffen in der Schweix mit Moosanalysen. Schriftenreihe Umwelt No. 194 - Luft, Bundesamt f-r Umwelt, Wald und LandschaR (BUWAL), Bern, p. 173. Siebert, A., I. Bruns, G.J. Krauss, J. Miersch and B. Markert, 1996. The use of the aquatic moss Fontinah antipyretica L. ex Hedw. as a bioindicator for heavy metals. 1. Fundamental investigations into heavy metal accumulation in Fontinaiis antipyretica L. Hedw. Sci. Total Environ. 177: 137-144. Siewers, U. and A.H. Roostai, 1990. Schwermetallbilanx aus Immission und geogenem Anteil im Einxugsgebiet der S&etalspemlHan, Ber. d. Forschungsxentrums Waldckosysteme,B 19, Giittingen. Sloof, J.E. and H.Th. Wolterbeek, 1991. A national monitoring survey using epiphytic lichens as biomonitors of traceelement pollution. Lichenologist, 23: 139-165.
Steinnes, E., J.P. Rambaek and J.E. Hanssen, 1992. Large scale multi-element survey of atmospheric deposition using naturally growing moss as biomonitor. Chemosphere, 25: 735-752 Steinnes, E., 1993. Some aspects of biomonitoring of air pollutants using mossesas illustrated by the 1976 Norwegian survey. In: B. Markert (Ed.), Plants as Biomonitors/ Indicators for Heavy Metals in the Terrestrial Environment. VCH Publisher, Weinheim, 1993, pp. 381-394. Wolterbeeck, H.Th., P. Kuik, T.G. Verburg, U. Herpin, B. Markert and L. Th6ni, 1995. Moss interspecies comparisons in trace element concentrations, Environ. Momt. Assess.,35: 263-286. Wittig, R., 1993. General aspects of biomonitoring heavy metals by plants. In: B. Markert (Ed.), Plants as Biomonitors/ Indicators for Heavy Metals in the Terrestrial Environment. VCH Publisher, Weinheim, pp. 3-28.
ELSEVIER
The German heavy metal survey by means of mosses B. MarkerPa, U. Herpinb, U. Siewers’, J. Berlekampb, H. Liethb, aIntematianal Graduate School (MI). Markt 23, D-02763 Zittau, FRG bInstitute for Environmental System Research, University of Osnabriick, Artilleriestrasse 34, D-4*76 Osnabriick. FRG cFederal Institute for Geosciences and Natural Resources, Stilleweg 2, D-30655 Hanrwver, FRG
Received 5 July 1995;accepted 2 November1995
Thisis the first attempt to determinepollution with metalsthroughoutthe FederalRepublicof Germanyby analysing mosssamples.Samplesof Pleurozium schreberi, Scleropodium ptuum, Hypnum cupessifotme and Hylocomitun splen&ns werecollectedat 593sitesand analysedby ICP-AES andAAS for the elements As, Cd, Cr, Cu, Fe, Ni, Pb, V andZn. Citrusleavesand pineneedleswereusedasreferencematerialsto ensurethe quality of the results.In many cases it waspossibleto trace the areasaffectedby known sourcesof heavy-metalemissions in addition to isolatedlocal increases in the values.The mossmonitoringprogrammeshowedup the highly industrializedand urbanlocationssuch asthe Ruhr, partsof the Garland and Baden-Wiitttembergand largeareasof easternGermany.Lowerlevelsof many elements werefound in wide stretchesof Lower Saxonyand Bavaria.The resultslargely reflect the pollution patterns found in theseareas.On the other hand,expectedcorrelationsbetweenthe effectsof traffic (e.g.Pb) andconcentrations in mosscould not bedemonstratedwith certainty. The elementdata yieldedby this projectare Germany’scontribution to the Europeanproject ‘AtmosphericHeavy Metal Depositionin Europe- Estimationsbasedon MossAnalysis’. Keywords: Biomonitoring;Heavy metals;Germany; Mosses;Survey
1. Introductiorl
The insidious accumulation of heavy metals over large areas and long periods, resulting in slow damage to living organisms, necessitates careful monitoringof the input, movements and effects of such pollutants. In recent years there has been a search for ways of determining heavy-metal deposition. The aim is to identify alternatives to conventional investiga* Corresponding author.
tion methods, especially in respect of precipitation,
as these are often very costly, fraught with analytical diff&&ies, and complicated by the inhomogeneous nature of precipitation. The new methods were to be simple, integral, representative and at the same time inexpensive (Fauth et al., 1985; Siewers and Roostai, 1990; Kuick et al., 1993; Bloemen et al., 1995). As the biologically effective results of pollution can only be determined by carrying out measurements on the organisms themselves, the most suitable indicator organisms are plants. Used as
0048-9697LW§15.00 0 1996ElsevierScience B.V. AI1rightsreserved SSDI 0048-9697195~05028-7
160
B. Markert et al. /The Science of the Total Environment 182 (19%) 159-168
‘bioindicators’, these plants show the effects of air pollution through reactions such as changes in population dynamics, development of certain damage symptoms and/or the accumulation of pollutant substances (Amdt et al., 1987; Bargagli, 1993; Djingova and Kuleff, 1993; Garty, 1993; Markert, 1993 and 1994b; Wittig, 1993). In the late 1960s the Swedish scientists Ake Rtlhling and Germund Tyler used mosses for monitoring the presence of heavy metals in the environment (Rtlhling and Tyler, 1968, 1970). They found that in particular Hylocomium splendens and Pleurozium schreberi are excellent ‘catch organisms’ for wet and dry depositions of heavy metals; in other words, certain mosses can be used as indicators of heavy-metal pollution. Since then, use of the mosses in this way for environmental monitoring has been systematically extended (Goodmann and Roberts, 1971; Ross, 1990, Steinnes et al., 1992; Brtining and Kreeb, 1993; Markert and Weckert, 1993, 1994; Steinnes, 1993; Siebert et al., 1995; Wolterbeek et al., 1995). The great majority of moss species were found to have the special advantage that they take the nutrients they require almost exclusively from the atmosphere, as they have not developed a real root system or water-conductive tissue (ectohydrous mosses). Heavy-metal uptake therefore takes place through the surface of the plants. Only in a few mosses such as the Polytrichum species the uptake of water and thus of heavy metals is assisted by an internal transpiration stream (endohydrous mosses). In the Federal Republic of Germany a research programme coordinated jointly by the Federal Government and the Lander (states) was started in 1990 on the lines of the monitoring progamme of the Scandinavian countries to determine the level of pollution caused by deposition of heavy metals and arsenic with the aid of moss analyses. The research project has the following objectives: (1) To establish and test a nationwide measurement network, taking the guidelines of the Scandinavian moss monitoring programme into consideration (2) To determine the regional extent of pollution with specific metals
(3) To identify problem areas and local sources of emissions (4) To establish a data base for comparative repeat studies at intervals of five years (5) To present the measurements in the form of maps. The present paper provides a brief summary of the results. Detailed results are to be found in the National Report (Herpin et al., 1994), which constitutes Germany’s contribution to the European project ‘Atmospheric Heavy Metal Deposition in Europe - Estimations based on Moss Analysis’. This again is part of the ‘European Monitoring and Evaluation Programme’ (EMEP: cooperative programme for monitoring and evaluation of the long-range transmission of air pollutants in Europe), (Sloof and Wolterbeek, 1991; SchmidtGrob et al., 1993; Rtihling, 1994). 2. Sampling, sample preparation and analytical performance Mosses were collected from 473 sites in West Germany and the southern parts of what used to be the GDR (East Germany) from September to November 1991. Normally only Pleurozium schreberi and Hylocomium splendenswere collected, but in the absence of both species Scleropodiumpurum or Hypmun cupressiformewas taken instead. In addition, 112 samples were taken from the northern parts of the former GDR in 1990. Following the sampling system of the Scandinavian team, 5-10 subsamples from each site (50 x 50 m) were taken on a random basis and finally mixed to make up a total sample. Only the upper three segments of Hylocomium splendensand the green or greenish-brown parts of Pleurozium schreberi, Scleropodium purum and Hypnum cupressiforme were collected. The unwashed samples were dried at 40°C and homogenized in an agate mill. The samples were digested with HNOs under pressure in closed quartz vessels and diluted with bidistilled water to make 40 ml. The concentrations were measured by AAS and ICP/AES. The quality of the results was ensured by measurement against the standard reference materials ‘citrus leaves NIST 1572’ and ‘pine
B. Markert et al. / Tke Science of the Total Environment 182 (1994) 159-168
needles NIST 1575’ (Markert, 1994a; Marker? et al., 1994). The heavy-metal levels were shown in the form of coloured contour maps using the coordinates of the sampling points (Figs. l-9).
161
lower than those of south-east Germany were measured in some parts of the Ruhr, the RhineMainRhine-Neckar area and north Germany. The As values of all the samples analysed range from 0.08 &g to 15.9 kg/g, the median being 0.28 pg/g.
3. Results ad discussion 3.1. Arsenic (Fig. 1)
The highest levels of As were found in the southem parts of east Germany close to the border with the Czech Republic, where there is a high level of industrialization in both states. In this region there is a large number of coal-fired power stations without proper filters, and also a chemical industry. A further important factor is the burning of coal in private homes in these densely populated urban areas, and this is a good indicator for the well-known high arsenic content of the brown coal of the Czech Republic and south-east Germany. Moreover, the high levels of arsenic near Freiberg and Aue can be explained by the existence of Ni smelters and a non-ferrous metal industry. Levels that were elevated, but nevertheless significantly
3.2. Cadmium (Fig. 2) Large-scale elevated cadmium levels were found in the western part of Germany (Ruhr), where there are Zn, Cu and Fe smelters, oil refineries and a chemical industry. High cadmium concentrations were also found around Stuttgart, which is a highly industrialized area, in the Han mountains where there is a long tradition of ore mining, and in the Freiberg/Aue region which is affected by the non-ferrous metal industry. Low background levels of cadmium were found in Lower Saxony and Bavaria. All cadmium values in this investigation were between 0.13 ccg/gto 0.87 c(g/g, with a median of 0.31 c(g/g. 3.3. Chromium (Fig. 3)
The distribution
Fig. 1. Contour map for the element As.
pattern for Cr shows areas with
162
B. Markert et al, /The Science of the Total Environment 182 (19%) 159-168
Cd Ipg/gl I a E3 I
c 0.2 0.3 0.4 0.6
:
0.6 0.7 - 0.7 0.6
:
0.9 > - 0.9
_ -
0.2 0.3 0.4 0.5 0.6
--I
0
60
loo
160
2oobn
Fig. 2. Contour map for the element Cd.
:
1.0 1.0< - 2.0
I
2.0 - 3.0
:
4.0 3.0 *- 4.0 6.0
:
6.0 -_ 6.0 7.0
:
7.0 > - 9.0 8.0
-
0
Fig. 3. Contour map for the element Cr.
1
50
100160200km
B. Markert et al. /The Science of the Total Environment 182 (19%) 159-W
cu [p&I/g1 <6
I
60 6 - 10 10 _ 12 12 - 14
: I I
14 16 - 16 16 - 20 > 20
Fig. 4. Contour map for the element Cu.
Ff? [j&l < 500 I I
n
500-1000 lwo-1500 1600-zoo0 2ooo-26ccl
I zfioo-3ooo 13orso-3600 :
3Wi7-4000 >4000
-
0
Fig. 5. Contour map for the element Fe.
c
60
loo
2
160
200 km
163
164
B. Markert et al. / Tke Science of the Total Environment 182 (19%) 159-168
elevated levels in the Ruhr and Saarland, where there are important metal industries, and in all parts of eastern Germany, especially in the Lausitz region. The highest levels were found in Brandenburg (steel production) and near Stralsund. Beside various industries and coal-fired power stations, the burning of coal in private households may be responsible for the elevated Cr levels. In particular fly ashes from combustion processes seem to irdluence Cr concentrations. Low concentrations of Cr were found in the south and north of Germany. All Cr values in the analysis were between 0.5 &g to 11.8 &g, the median being 1.8 fig/g. 3.4. Copper (Fig. 4)
The distribution of Cu identifies a number of emission sources all over Germany, characterized by many well-known local sources. Examples are the copper smelters in the north of the Ruhr and a facility near Hamburg. Other important sources are the metal-working factories around Stuttgart. High local values were found near Bamberg and Wilrzburg. Generally speaking, the Cu levels found in the eastern parts of Germany are higher than those of the Ruhr. The Cu concentrations in Lower Saxony are low. All Cu measurements range between 4.1 &g to 25.5 &g, the median being 9.1 fig/g. 3.5. Iron (Fig. 5)
A comparison between west and east Germany reveals considerably higher levels in the southeastern parts, especially in the industrial area close to the Polish border. Important sources here include the ironworks near Eisenhiittenstadt and Riesa and the coal mining activities of the region. An elevated local value was found to the north of NurembergErlangen. Higher background levels in the Ruhr may be explained by the iron smelters in this area. Lower values were found in large parts of Bavaria, Lower Saxony and the south of BadenWtirttemberg. In general it should be noted that soil particles and fly ashes may influence the iron content of mosses. All Fe values ranged from 153 &g to 6257 j&g, with the median of 556 &g. 3.6. Nickel (Fig. 6)
The pattern of Ni distribution
is characterized
by elevated levels in the western and south-western parts of Germany, for example the Ruhr, the Rhine-Neckar region, the south-western parts of Baden-Wiirttemberg near Base1 (Switzerland), and the Saarland. In eastern Germany, high levels were found in Schwedt (refineries) and near the coast. The reason for the elevated concentrations is the importing of Nicontaining rock phosphate from Kola (CIS). In all the above areas high nickel concentrations reflect the possible influence of oil consumption, accumulations of power stations and various metal-working industries. Low concentrations were found in the northern parts of Lower Saxony and the south of Bavaria. The values range from 0.56 &g to 16.0 fig/g, with a median of 2.38 P&3* 3.7. Lead (Fig. 7)
Elevated Pb concentrations were found in the densely populated and industrialized western, south-western and eastern parts of Germany. The highest values were found near Rastatt and Freiberg, reflecting the non-ferrous metal working industry. In some cases it was not possible to detect a relationship between Pb patterns and traffic density. Nor was it possible to make definite statements on the inlluence of industry in the Frankfurt and Munich regions. The Pb values were between 5.1 pglg and 80.5 &g, the median being 12.9 pg/g. 3.8. Vanadium (Fig. 8)
The pattern of background levels of V is similar to that for the distribution of Ni and shows elevated levels in the Ruhr and large parts of eastern Germany, especially Saxony and Brandenburg. Local maxima were observed in the vicinity of Karlsruhe/Gaggenau, where there is a high density of oil refineries on both the German and French side of the border, and to the north of Nuremberg/Erlangen. High values were measured on the refinery sites near Schwedt. The high vanadium concentration in this area may be due to imports of V-enriched crude oil from the CIS. The high levels in the eastern parts of Germany may be influenced by coal burning and the considerable industrial activity along the border with Poland and the Czech Republic. Lower values were found
B. Markert et al. / The Science of the Total Environment 182 (1996) 159-168
Ni [m/g1 3
,.5;- z
I
2.26 - 3.00 3.00 - 3.76 3.75 _ 4.50
I m
4.50 5.26
:
6~oo >- 6.75 6.76
--I 0
w
_ 6.26 - 6.00
100
160
Fig. 6. Contour map for the efemc:nt 1G.
m r&31 :
100 16 20 26 30
:
: I
0
Fig. 7. Contour map for the element Pb.
-_ 10 16 - 20 - 2s - 35 30
36-40- 46 40 > 46
60
lfJo160203km
2cokm
165
B. Markert et al. /The Science of the Total Environment 182 (19%) 159-168
m
m m
< 2.0 3.0 4.0 5.0 6.0
: m
9.0 7.0 _- 9.0 > 9.0
m
2.0 _ 3.0 4.0 - 6.0 - 6.0 - 7.0
3
0
60
loo
150
wokm
Fig. 8. Contour map for the element V.
: m
40 <- 40 50 50 - 60 6070
:
70 90 - 90
m m
90 - 100 100 - 110
m
>
-
0
Fig. 9. Contour map for the element Zn.
110
-
60
’
loo
180
200 km
B. Markert
et al. /The
Science
of the Total Environment
in the south of Germany, for instance in Bavaria and Baden-Wiirttemberg. All values for vanadium were between 0.5 &g and 13.6 @g/g; the median was 2.86 &g. 3.9. Zinc (Fig. 9)
The highest large-scale levels were found in the Ruhr, where there is a considerable concentration of Zn, Cu and Fe smelting. Moreover, the pattern of Zn distribution showed increased concentrations in other densely populated and highly industrialized regions of western and south-western Germany, for example the surroundings of Stuttgart, the Rhine-MairVNeckar area and the Saarland. Elevated levels were also found in the industrialized areas of the Harz Mountains and around Berlin. Lower values were found in Bavaria, Thuringia and Lower Saxony. The highest values were measured in Senftenberg and Hoyerswerda, and these cannot be explained at the moment. In all, the Zn values ranged from 23.7 &g to 396 &g with a median of 50.4 &g. Acknowledgements We wish to thank the members of the study group ‘Bioindication and Analysis of Effects’ for their assistance during the sampling period. This is a project (UBA-FB 94125/108 02 087) founded by the Federal Environmental Agency in the Environmental Research Plan of the Federal Environment Ministry). Dr. Bau of the UBA is thanked for overall coordination of the project and Mrs. M. Braase (Buchholz, FRG) for the English translation. References Amdt, U., W. Nobel and B. Schweitzer, 1987. Bioindikatoren, Mi?@ichkeiten, Grenaen und neue Erkenntnisse, Verlag Eugen Ulmer, Stuttgart, p. 388. Bargagb, R., 1993. Plant leaves and lichens as biomonitors of natural and anthropogenic emissions of mercury. In: B. Markert (Ed.), Plants as Biomonitora&tdicators for Heavy Metals in the Terrestrial Environment, VCH Publisher, Weinheim, 1993, pp. 461-484. Bloemen, ML., B. Markert and H. Lieth, 1995. The distribution of Cd, Cu, Pb and Zn in topsoils of Gsnabrijck in relation to land use. Sci. Total Environ., 166: 137-148. Btining, F. and K.H. Kreeb, 1993. Mosses as biomonitors of
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heavy metal contamination within urban areas, In: B. Markert (Ed.), Plants as Biomonitors/Indicators for Heavy Metals in the Terrestrial Environment. VCH Publisher, Weinheim, 1993, pp. 395-402. Djingova, R. and I. Kuleff, 1993. Monitoring of heavy metal pollution by Taraxacwn officinale. In: B. Markert (Ed.), Plants as Biomonitotindicators for Heavy Metals in the Terrestrial Environment, VCH Publisher, Weinheim, 1993, pp. 435-460. Fauth, H., R. Hindel, U. Siewers, J. Zitmer, 1985. Geochemischer Atlas Bundesrepublik Deutschland - Verteilung von Schwermetallen in W&em und Bachsedimenten, Brmdesanstalt fiir Geowissenschaften und Rohstoffe, Schweizerbart’sche Verlagsbuchhandlung (Nigele und Obermiiller), Stuttgart. Garty, J., 1993. Lichens as biomonitors for heavy metal pollution. In: B. Market? (Ed.), Plants as Biomonitors/ Indicators for Heavy Metals in the Terrestrial Environment. VCH Publisher, Weinheim, 1993, pp. 193-264. Goodmann, G.T. and T.M. Roberts, 1971. Plants and soils as indicators of metals in the air, Nature, 231: 287-292. Herpin, U., B. Marker& U. Siewers and H. Lieth, 1994. Monitoring der Schwermetallbelastung in der Bundesrepublik Deutschland mit Hilfe von Moosen. Forschungsbericht 108 02 087 im A&rag des Umwehbundesamts, Berlin, 161 S. Kuick, P., M. Blaauw, J.E. Sloof and H.Th. Wolterbeek, 1993. Application of Monte-Carlo assisted factor analysis to large sets of environmental pollution data. Atmos. Environ., 27A(13): 1975-1983. Markert, B. (Ed.), 1993. Plants as Biomonitors/Indicators for Heavy Metals in the Terrestrial Environment, VCH Publisher, Weinheim, p. 640. Markert, B. (Ed.), 1994a. Environmental Sampling for Trace Analysis. VCH Publisher, Weinheim, p. 524. Markert, B., 1994b. Biomonitoring - Quo Vadis? Z. Umweltchem. Gkotox., 6(3), 145-149. Marker& B. and V. Weckert, 1993. Tie-and-site integrated long-term biomonitoring of chemical elements by means of mosses. Toxicol. Environ. Chem., 40: 43-56. Markert, B. and V. Weckert, 1994. Higher lead concentrations in the environment of former West Germany after the fall of the ‘Berlin Wall’. Sci. Total Environ., 158: 93-96. Marker& B., U. Reus and U. Herpin, 1994. The application of TKRF in instrumental multielement analysis of plants, demonstrated with species of moss. Sci. Total Environ., 152: 213-220. Ross, H., 1990. On the use of mosses (Hylocomium splendens and Pleurozium schrebert) for estimating atmospheric trace metal deposition. Water, Air and Soil Pollution, 50: 63-76. Riihiing, A. and G. Tyler, 1968. An ecological approach to the lead problem. Botaniska Not&r, 122: 248-342. Riihling, A. and G. Tyler, 1970. Sorption and retention of heavy metals in the woodland moss Hylocomium splenah (Hedw.). Br et Sch. Oikos, 21: 92-97. Riihling, A. (Ed.), 1994. Atmospheric heavy metal deposition in Europe - estimations based on moss analysis. Nord 199419.
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S&mid-Grob, I., L. Th6ni and J. Hertz, 1993. Bestimmung de.r Deposition von Luftschadstoffen in der Schweix mit Moosanalysen. Schriftenreihe Umwelt No. 194 - Luft, Bundesamt f-r Umwelt, Wald und LandschaR (BUWAL), Bern, p. 173. Siebert, A., I. Bruns, G.J. Krauss, J. Miersch and B. Markert, 1996. The use of the aquatic moss Fontinah antipyretica L. ex Hedw. as a bioindicator for heavy metals. 1. Fundamental investigations into heavy metal accumulation in Fontinaiis antipyretica L. Hedw. Sci. Total Environ. 177: 137-144. Siewers, U. and A.H. Roostai, 1990. Schwermetallbilanx aus Immission und geogenem Anteil im Einxugsgebiet der S&etalspemlHan, Ber. d. Forschungsxentrums Waldckosysteme,B 19, Giittingen. Sloof, J.E. and H.Th. Wolterbeek, 1991. A national monitoring survey using epiphytic lichens as biomonitors of traceelement pollution. Lichenologist, 23: 139-165.
Steinnes, E., J.P. Rambaek and J.E. Hanssen, 1992. Large scale multi-element survey of atmospheric deposition using naturally growing moss as biomonitor. Chemosphere, 25: 735-752 Steinnes, E., 1993. Some aspects of biomonitoring of air pollutants using mossesas illustrated by the 1976 Norwegian survey. In: B. Markert (Ed.), Plants as Biomonitors/ Indicators for Heavy Metals in the Terrestrial Environment. VCH Publisher, Weinheim, 1993, pp. 381-394. Wolterbeeck, H.Th., P. Kuik, T.G. Verburg, U. Herpin, B. Markert and L. Th6ni, 1995. Moss interspecies comparisons in trace element concentrations, Environ. Momt. Assess.,35: 263-286. Wittig, R., 1993. General aspects of biomonitoring heavy metals by plants. In: B. Markert (Ed.), Plants as Biomonitors/ Indicators for Heavy Metals in the Terrestrial Environment. VCH Publisher, Weinheim, pp. 3-28.