Pergamon Applied Geochemistry, Vol. 11, pp. 149-154, 1996

Copyright 0 1996 Elsevier Science Ltd Printed in Great Britain. All rights reserved

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Atmospheric element input in the Eastern Ore Mountains

J&g Matschullat and Elke Bozau Institute for Environmental Geochemistry, University of Heidelberg, Im Neuenheimer Feld 236,

D-69120 Heidelberg, Germany

Abstract-The element input by atmospheric deposition to the 104 km2 catchment of the Rote WeiBeritz, Saxonia, Germany, was regularly monitored from 1992 to 1994. Median values for bulk deposition are: H + 0.57,Nal 3.5, Kf 2.5, Ca + 4.6, Mg2+ 1.1, NH4+ ~7, F- cO.9, Cl- 6.3,POd3- ~4, NO,- 5.2, Sod- 14.7, A13+ 0.54, Fe3+ cO.9, Mn2+ ~0.4, Zn2+ 0.27 (kg ha-’ a-‘) and Cd cO.9, Co < 14, Cr ~4, Cu < 18, Ni <9, Pb 36 (g ha-’ a-‘). The atmospheric input data are comparable with other data from central Europe and show the same trend of declining concentrations for many components. A comparison of the given concentrations with local drinking water and the German drinking-water standards illustrates the severe threat to local wells by contaminated ground- and surface-water, especially in respect to pH, Al, and to a lesser degree Fe, Mn, Cd, and Pb. According to a first mass balance, Al, Fe, Mn, Zn, and Cu are in import-export equilibrium within the catchment. Cadmium is being exported at a higher rate whereas Pb is retained in the system and most probably stays with Pb-organiccomplexes in soils and sediments. Copyright 0 1996 Elsevier Science Ltd _ . .

INTRODUCTION

Since 1991 the German Science Foundation has supported the Pilot Study Eastern Ore Mountains, an interdisciplinary research project. Geologists, geochemists, limnologists, and soil scientists follow the fate of environmental indicators from atmospheric deposition via soils and soil solutions, surface waters, and sediments to aquatic biota and drinking-water quality (Matschullat et al., 1994a). Within the 104 km2 catchment of the Malter reservoir (Dippoldiswalde, Saxonia, Germany), five collector stations monitor the atmospheric input (both canopy throughfall and bulk deposition; Fig. 1; Bozau, 1995). After a two- year sampling period (1992 through 1994), a total of 44 bulk samplers, two active low volume filter samplers (for particulate input) and several bog cores provide a fair estimate or the weekly/monthly input (from samplers) and of the historical input respec- tively (from bog cores).

METHODS

Total deposition collectors were used f r bulk and throughfall deposition, including snow bucl ts in winter (Meiwes et al., 1984; Winkler et al., 1989) and low volume samplers for atmospheric dusts (VDI 2463 B8, 1980). Results for both the bog core investigations and the dust samplers will be presented in later publications. The rainwater samples were split for anion and cation analysis respectively after the field determination of temperature (“C), pH-value and conductivity (pts cm-‘). A sample aliquot for anions was stored frozen (- 18”C), and an aliquot for cations was acidified with concentrated HNOs p.a. to pH 2. All samples had been decanted or filtered (0.45 pm) prior to analysis.

The determination of all major cations was performed with flame atomic absorption spectrometry (Na+, K+, Ca2+,

Mg*+) and spectrophotometry (NH4+). The anions (F-, Cl-, N03-, P04’-, SOd2-) were determined by ion chromatography, and the trace components (Al, Cd, Cr, Co, Cu, Fe, Ni, Pb, and Zn) by graphite furnace AAS. Analytical errors were usually below 3% for major and below 10% for minor and trace components. With concentrations at the limit of detection, errors of up to 100% have to be accepted. The respective results and/or calculations are given in parentheses. Much more important than the analytical errors are the inherent variations between different sampling devices and sampling in general (Ulrich et al., 1986; Winkler ef al., 1989). Thus, we anticipate a total error of up to 30% even for major components and up to 100% for trace elements.

RESULTS AND DISCUSSION

Table 1 lists the concentration values both for bulk and throughfall deposition for the whole period. Noteworthy is the high variance typical for atmo- spheric deposition. Deviations from the mean are up to one-order of magnitude for trace components and up to two-orders of magnitude for major components. These variations are due to irregular deposition patterns, rainfall, and wind activity. The example of lead within an annual cycle illustrates this even further (Fig. 2). This emphasizes the necessity for longer term monitoring of atmospheric deposition, if representa- tive data are to be gathered.

Acidic deposition, in combination with rather thin soils and low buffering capacities, leads to the acidification of shallow ground- and surface-waters. The acidic water leaches cations from soils and sediments, accelerates the corrosion of pipes, and eventually reaches private drinking-water supplies (Heinrichs et al., 1994; Steiner, 1994). A comparison of the given concentrations from atmospheric deposi-

149

150 J. Matschullat and E. Bozau

a collector station for atmospheric deposition

Welder Hochmoor

5km

Fig. 1. The Malter catchment area with collector stations for atmospheric deposition.

tion with concentrations from local drinking water from private wells and with the German drinking- water standards illustrates the severe threat to local wells in shallow aquifers (Table 2). The pH-values and Al concentrations exceed the allowed thresholds. Also Fe, Mn, Cd, and Pb pose a potential problem to local small-scale drinking-water systems. Authorities are already aware of the situation but lack the funding to immediately solve it.

The element concentrations from atmospheric deposition translate into mass flows (mass ha- ’ a- ‘) which may characterize the influx to the whole catchment (Table 3). The distribution of open land (cu 66%) and forests (ca 33%) leads to an equivalent percentage for bulk and for throughfall deposition with an estimated annual rainfall rate of 900 mm for

the sampling period. The resulting input in the Eastern Ore Mountains largely corresponds to other mountai- nous areas in central Europe (e.g., Bayerischer Wald, Gietl and Rall, 1986; Black Forest, Mies and Zotte, 1986; Harz, Andreae, 1994; Jizera, Cerny, 1993; Odenwald, Evers, 1985, etc.). Figure 3 depicts the local deposition in perspective. The bulk deposition data for Europe are from Ftihrer et al. (1988). Their data base is from the late seventies to the mid eighties. The lower inflow for the catchment clearly shows the general decrease of most components from atmo- spheric deposition over the past 20 years.

With the exception of K and Mn, the atmospheric input can be explained by long range transport. Its chemical “fingerprint” resembles analogous data from Europe. After a long period of severe atmo-

Atmospheric element input in the Eastern Ore Mountains

Table 1. Concentration ranges and median values for bulk samplers

151

Bulk precipitation (n = 135)* Throughfall precipitation (n = lo’)?

Minimum Maximum Median Minimum Maximum Median

PH Cond. ($ cm-‘) Na’ (mg 1-l) K+ Ca’+ Mg’+ NH4’ F- cl- POJ3 - NO%_ so4 - A13+ Fe3+

Cd (a I-‘) co Cr cu Ni Pb

3.0 17 0.05 0.06 0.09 0.02

<O.lO <O.lO <O.lO <OS0 <0.50

0.28 <0.05 <O.lO <0.05 <O.Ol <O.lO <0.50 <0.50 <2 <l.O <l.O

8.2 4.2 395 50

5.7 0.39 6.2 0.28 8.0 0.51 3.6 0.12

16.0 1.0 0.6 <O.l 8.9 0.7 5.9 <0.5

18.6 2.54 28.3 4.91 0.9 0.06 0.37 <O.l 0.12 <0.05 0.28 0.03 7.0 10.1 1.0 <0.50 3.0 <0.5

20 <2 28 <l 21 4

2.5 7.3 27 1060 0.12 7.6 0.12 50.6 0.2 12.0 0.1 4.6 0.5 7.8

<O.l 1.9 0.65 15.9

<0.5 5.1 <0.5 81.9

1.1 82 <0.05 1.2 <O.l 1.6 <0.05 1.17 <O.Ol 0.26 <O.lO 2.0 <0.50 0.7 <0.50 6.0 <2 18 <l 13 <I 32

3.7 190

0.89 3.02 2.53 0.47 1.9 0.25 1.87

<OS 6.57

20.5 0.3 0.16 0.15 0.05 0.3

<0.5 0.6 2.0 2.0

Bulk precipitation (open land) was collected at stations I, II, III, and IV, while canopy throughfall was collected at stations II, III, and V (Fig. 1; Bozau, 1995). *Number of bulk precipitation samples for Co, Ni, and NH4 is 62,6 1, and 60. TNumber of canopy throughfall precipitation samples for Co, Ni, and NH4 is 49,47, and 46, respectively.

spheric stress which led to the acidification of soils and headwaters in most forested mountainous regions and the subsequent decline of (mainly spruce) forests on the mountain tops, the input of sulphur and some trace elements seems to decline - a tendency which can be observed almost anywhere in central Europe - due to improved emission control. Nevertheless, sulphate immissions are still high, and so are those of

25

20

15

10

5

0

trace components such as As, Cr, Cu, Fe, Ni, Pb, and V (Rtihling, 1994).

The input data help to estimate the element flux in the Rote WeiDeritz catchment and can be linked to data from particulate and solvent transport, soil processes, and sediment accumulation as well as limnology. Figure 4 displays a first mass balance for the influx (atmospheric deposition) and output from

bulk

0 throughfall

Feb. Apr. June Aug. Dec.

Fig. 2. Lead concentration in bulk and throughfall precipitation and its annual variation in 1993 (station II. Piibelbach).

152 J. Matschullat and E. Bozau

Table 2. German drinking-water threshold values, atmospheric deposition and local drinking-water quality in the Eastern Ore mountains

(Ke? 1-l) TV0 (1990)*

Threshold values Precipitation collectorst

Minima Maxima Drinking water1

Minima Maxima

PH 6.5-9.5 Al 200 Cd 5 Cr 50 cu 3000 Fe 200 Mn 50 Ni 50 Pb 40 Zn 5000

2.5 8.2 <50 1200

<O.l 7.0 <0.5 6.0 <l.O 20

<70 1600 <50 1170

<l.O 28 <l.O 32 10 280

4.3 7.6 <40 7

2 20 10.1 1

0.3 400 2 4000

<5 700 1 40

<0.5 100 <lO 3300

*German drinking-water standards (TVO) from 1990. tThis work. $Data: Steiner (1994); n = 108.

the catchment (defined as particulate and dissolved element input into the Malter reservoir from its main tributary, the Rote WeiDeritz stream, which drains 77% of the catchment (Matschullat et al., 1994a).

While the influx of atmospheric Al, Fe, Mn, Cu, and Zn seems to be in equilibrium with the catchment export, Cd is being exported at a much higher rate. Lead seems to be retained in the system; its influx exceeds the outflow by an order of magnitude. Al, Fe, and Mn are major components of the earth’s crust and thus potentially related to natural dusts. At the same time, higher concentrations of these metals occur in urban particulates (Lantzy and Mackenzie, 1979), together with enrichments of Cu, Pb, and Zn. Owing

to its strong affinity to organic complexation, Pb seems to be kept within the system by Pb-organic complexes mainly in the soils and in the sediments. Cadmium reacts conversely and is easily released from most of its non-mineral bonds (Andreae, 1994; Hild, 1993; Matschullat et al., 1994a; Matschullat et al., 1994b; Schubert, 1993).

CONCLUSIONS

Though a decreasing trend can be shown for many components of inorganic atmospheric deposition, the aerial input is still high within central Europe.

Table 3. Input of major and minor components (kg ha-’ a-‘), and trace elements (g ha-’ a-‘). Median values for the two-year period from May 1992 to April 1994 (24 sampling

months)

(bd) I, II, III, IV* (td) II, III? FS &A§

H Na K Mg Ca NH4-N F Cl PO4 NO,-N so4-s

Al Fe Mn Zn Cd co Cr CU Ni Pb

0.57 1.8 3.5 8.0 2.5 27.2 1.1 4.2 4.6 22.8

(7) 13.3 (0.9) 2.3 6.3 16.8

(4) (4) 5.2 13.4

14.7 61.2 0.54 2.7

(0.9) 1.44 (0.4) 1.35

270 450 (0.9) 2.7 (4) (4) (4) 5.4

(18) 18 (9) 18 36 63

3 2

11 4

(:) (3)

(:) 3 4 5

(2) (3)

(:) (1) (1) (1) (;)

1.5 5.0

10.6 2.1

10.6 (9) (1.4) 9.7 (4) 7.9

30.0 1.2

(1.1) (0.7)

326 (1.5) (4) (4)

(18) (11) 44.6

Values in parentheses represent data from Table 1 with concentrations below the detection limit. *Bulk deposition (roman numerals refer to the collector stations; Fig. 1). tCanopy throughfall deposition (roman numerals refer to the collector stations; Fig. 1). IRounded factor td/bd. §Catchment area with 66% bulk deposition and 33% throughfall deposi- tion.

Atmospheric element input in the Eastern Ore Mountains 153

000

Doe

100

10

Fig. 3. Total deposition (g ha-’ a-‘) in the Eastern Ore Mountains (0) compared with the range for Europe (data

compiled after Fiihrer et al., 1988).

Elements which are directly related to the use of fossil fuels (e.g. S and Pb) exhibit a distinct annual variation with winter highs (heating period) and summer lows. The strong acidification of many soils and most fresh waters leads to a high mobilization rate of the base cations and many heavy metals, and their subsequent depletion especially in the soils. This “leaching” in turn, negatively influences many private drinking-

100

IO

Al Fe Mn Zn Cd . Cu . Pb

Fig. 4. Comparison of the atmospheric deposition influx with the output range, where Output 1 = low discharge and Output 2 = high discharge from the catchment in dissolved and particulate form, given in tons per year. At low discharge, 550 1 s-’ are being led into the Malter reservoir,

whereas 2900 I s-’ pass through at high discharge.

water wells, which are unsafe in respect to Al and pH-values and may cause problems with Cd and Pb. An additional uncertainty concerns the rather strong eutrophication of some headwaters and the Malter reservoir itself (Matschullat et al., 1994). The next step of our research will focus on the more detailed modelling of atmospheric input and the reactions and pathways of the potential pollutants in the soil/ water system.

Acknowledgements-The authors are indebted to the German Science Foundation for their financial support (DFG-Ma 1414/l-2) and wish to express their thanks to the two anonymous referees whose constructive criticism helped to improve the quality of the paper. We also gratefully acknowledge the infrastructural support, both from the staff of the Malter reservoir water authorities and the meteror- ological station at Zinnwald.

Editorial handling: Dr 0. Selinus

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