Mineral and nutrient supply, content and leaching in Norway spruce exposed for 14 months to ozone and acid mist

Environmental Pollution 64 (1990) 229-253

Mineral and Nutrient Supply, Content and Leaching in Norway Spruce Exposed for 14 Months to Ozone and Acid Mist T. Pfirrmann lnstitut fi.ir BiochemischePflanzenpathologie, Expositionskammern, GSF Miinchen, Ingolst~idter LandstraBe 1, D-8042 Neuherberg, FRG

K.-H. Runkel," P. Schramel b & T. Eisenmannb Institut fiir Toxikologie, h Institut ffir ~kologische Chemie, Zentrale Analytik, GSF Mfinchen, Ingolst~idterLandstrai3e 1, D-8042 Neuherberg, FRG

A BSTRA CT The nutrient contents o f an acid and a calcareous soil, as well as the foliar contents of four clones o f Norway spruce grown on these soils, were evaluated during a 14-month exposure to loB' level ozone ( 100 pg m - 3 + peaks between 130 and 360/~gm - 3 ) plus acid mist (pH3.0). Whilst distinct differences could be established between and within clones depending on soil types and genoO'pe, only f e w pollutant-related effects were observed. Leaching losses f r o m Joliage were generally low compared to.field studies. The data obtained with young trees in an artificial environment do not support the hypothesis that enhanced leachingJ?omjoliage may contribute to nutrient deficiencies in mature stands o f Norway spruce.

INTRODUCTION During the last decade, widespread symptoms of damage and forest decline have been reported for coniferous and broadleaved trees throughout Europe (Forschungsbeirat, 1986). It is currently considered that complex interactions between natural and anthropogenic stresses are responsible for the recent decline of N o r w a y spruce (Picea abies [L.] Karst.) growing on acidic brown earth soils at high altitude ( > 800 masl) in Bavaria. Elevated ozone concentrations, frequent events of acidic mist, extreme climatic events 229 Environ. Pollut. 0269-7491/90/$03"50 ~) 1990 Elsevier Science Publishers Ltd, England. Printed in Great Britain

230

T. Pfirrmann et ai.

(e.g. frost shocks and drought), soil-specific nutrient disorders (e.g. Mg and/or K deficiency), atmospheric nitrogen deposition and unfavourable site conditions (e.g. steep slopes, shallow stoney soils) may act together resulting in foliar deficiencies of Mg and/or K, premature senescence of older needles and eventually death of single trees and whole stands of spruce (Bosch et al., 1983; Rehfuess, 1983, 1985, 1987). One of the characteristic symptoms of'Type 1' decline (Mg deficiency) and 'Type 4' decline (K deficiency) is a distinct chlorosis of the upper surface of older needles (Zech & Popp, 1983). Leaching of nutrient elements from foliage, as well as from the root zone, is considered to contribute towards the symptoms of foliar-nutrient deficiency (Roberts et al., 1989). However, whilst field studies on leaching have yielded much information regarding the turnover of elements in forest canopies (Lakhani & Miller, 1980; Cronan & Reiners, 1983; Matzner, 1984, 1988), this methodology has certain limitations when the objective of the experiment is to define causal relations. For instance, it is not possible to reliably distinguish between dry deposition and leaching from foliar tissue in field studies (Lindberg et al., 1986), and furthermore, the chemistry of rain droplets may change rapidly in the field (Haines et al., 1980). In contrast, laboratory based experiments enable mist chemistry to be controlled. Such studies have revealed that exposure of conifers to acid mist can result in degradation of the surface waxes (Mengel et al., 1987; Barnes & Brown, 1989), changes in photosynthesis (McLaughlin, 1988), disturbances in needle water relations (Mengel et al., 1989; Barnes et al., 1989) and cause visible damage (Blank & Skeffington, 1985; Mengel et al., 1987). In order to investigate the role of interactions between acid mist, ozone and soil nutrient status in spruce decline, as proposed by Rehfuess & Bosch (1986), a long-term integrated study was conducted in controlled environment chambers at the GSF. This paper reports the part of this study investigating the effects of a 14-month exposure to ozone and acid mist on the nutrient status of needles of Norway spruce trees grown on two contrasting soils. This study included an analysis of throughfall in order to investigate whether exposure to acid mist and ozone increased foliar leaching.

MATERIALS A N D METHODS

Soil and plant material In order to simulate two typical field sites in Southern Bavaria, two different soil types have been used in the experiment: an acid (original pH 4"5) sandy

Mineral and nutrient supply in Norway spruce

231

soil obtained from a natural spruce stand in the Neureichenau/Bavarian Forest (herein referred to as soil 1), and a calcareous soil (original pH 6.8) obtained from a forest in the Bavarian Alps near Schliersee (herein referred to as soil 2). Soil 1, classified as a Dystric Cambisol derived from granite (Rehfuess & Bosch, 1986; Bosch et al., 1986) was collected from the Bhorizon (approximately 10-14cm depth), roughly mixed and then passed through a 2-cm sieve. Soil 2, classified as Rendzina derived from Hauptdolomite, was collected from the A- and C-horizons (approximately 0--20cm depth) and then roughly mixed but not sieved. Three-year-old clonal trees originating from Southern Bavaria midaltitudinal provenance were repotted as bare-root cuttings in April 1985 into pots containing 21itres of soil. Plants were raised outside in a nursery (Staatliche Samenklenge und Pflanzgarten, Laufen, FRG), where they were irrigated with water from the river Salzach. In April 1986, trees were transferred to controlled environment chambers at the GSF (Blank et al., 1990), where they were watered from an ion exchange unit via glass fibre strings (8 m m diam.) fed from a reservoir beneath each plant. This enabled the amount of water applied to each individual tree to be recorded. The irrigation system was allowed to maintain soil moisture and water tension in the range of field capacity for most of the time, but occasionally watering was deliberately interrupted for 3-4 days in order to emulate natural conditions, particularly during winter and early spring. Evaporation was prevented by fitting polyethylene covers over the surface of each pot. These covers permitted gas exchange to the soil, but prevented percolation of throughfall into the soil whilst also enabling it to be collected in a perspex tray connected to a sampling bottle. Ozone and mist treatments

Trees were exposed in duplicate chambers to either a background level of ozone ( 5 0 p g m -3) or to an elevated level of ozone (100#gm 3 plus seasonally varying peaks of 130-150#gin -3 for 1-2 days every 1-2 weeks) from July 1986 to September 1987. Trees in the low ozone treatment were exposed to control mist (pH 5-6), whilst trees in the elevated ozone treatment received acid mist (pH 3"0). Mist was applied for 8-10 h overnight from eight glass nozzles positioned in the walls of each chamber (for details see Blank et al., this issue). Misting periods of three or four consecutive nights were followed by several days without mist events. During the 1987 fumigation, mist was applied equivalent to a total precipitation of 90-120 mm. During winter (between December and April) no mist was applied. Mist solutions were prepared by dissolving sodium sulphate in distilled water (29 mg litre- ~) to provide precipitation with an ionic strength comparable to

232

T. Pfirrmann et ai.

that in the field (Bosch et al., 1986). Solutions were adjusted to pH 3.0 or pH 5-6 using sulphuric acid or sodium hydroxide. All other elements collected in throughfall originated from wash-off or leaching from above ground plant tissue. The sophisticated air filtering system fitted to the chambers (Roberts et al., 1987) reduced dry deposition, dust, contaminant gases, vapours and aerosols to a minimum. The level of background deposition was actually quantified from 'blank' leachates collected from artificial nylon trees. Throughfall was collected and 25-ml aliquots were analysed using an Atomic Absorption Spectrometer for Ca, K, Mg, Na, Mn, Fe and Zn. All values were corrected for the levels of specific elements in 'blank' leachates collected from plastic trees. Estimates of total leaching in the second year were calculated by multiplying the concentration of specific elements by the volume collected over the previous 21 mist events.

Fertilizer applications Several fertilizer applications (see Table 1) were made during the period of the experiment, in order to avoid or overcome unexpected foliar deficiencies of major (N, P, S) and trace (Cu, Fe, Mn and Zn) nutrients, which were not associated with soil specific nutrient conditions. Fertilizers were dissolved in distilled water and watered into the rooting zone. Ca, Mg and K were deliberately excluded from fertilizers in order to maintain soil specific nutrient disorders.

Soil analysis At the end of the experiment (14 September 1987), pots in which two clones (Nos I1 and 14) had been grown were selected for soil analysis. Coarse material (> 2 mm diam.), fine soil ( < 2 ram) and total below ground biomass were separated and then weighed after drying for 2 days at 105°C. Extracts of 10 g fine soil were shaken overnight in 25 ml 0"1M KC1, allowed to settle for 2 h and then soil-pH was determined using a glass electrode. Exchangeable cations were determined in percolates of 2.5g fine soil and 100ml of unbuffered IMNH4C1, as described by Meiwes et al. (1984). The NH4C1 technique was performed so that methodological conditions were comparable to other data in the literature even though this technique may have overestimated the exchange capacities of soil 2 due to carbonate dissolution by the NH4C1. Element concentrations in the percolate samples were determined by ICP-analysis (Schramel, 1988). All analyses were carried out on two replicates of each sample. Effective cation exchange capacity (CECefl) was calculated from the sum of the equivalents of the exchangeable

Mineral and nutrient supply in Norway spruce

TABLE

233

1

Fertilizer Treatments during the Experiment Year

Date

Soil

Element

1986

a-d a-d a-c a-c d d e e e e e e e e

1 2 1 2 1 2 1 2 1 2 1 2 1 2

N N P P S S Cu Cu Fe Fe Mn Mn Zn Zn

1987

fh f-g h

1 2 1

N N P

--

2

P

h

1

S

--

2

S

f f f f f f

1 2 1 2 1 2

Cu Cu Fe Fe Mn Mn

Total amount

126"1 92"9 100"0 81"5 4-65 4-65 5"0 5.0 50.0 50-0 50-0 50.0 10.0 10"0 1 640 1 500 33-2

Chemical composition

NH4NO3; (NH4)HzPO4; (NH4)2SO4 NH4NO3; (NH4)H/PO4; (NH4)2SO4 (NHg)HzPO4 (NHg)H2PO4 (NH4)2SO 4 (NH4)2SO 4 Cu-chelate* Cu-chelate* Fe-chelate* Fe-chelate* Mn-chelate* Mn-chelate* Zn-chelate* Zn-chelate* NH4NO3: (NH4)H2PO4; (NH4)2SO4 NH4NO 3 (NH4)H2PO 4

-

20"7 -50-0 50.0 200.0 200.0 200.0 200.0

(NH4)2SO 4 Cu-chelate* Cu-chelate* Fe-chelate* Fe-chelate* Mn-chelate* Mn-chelate*

Dates: a: 07-08/09-86; b: 08-30/31-86; c: 11-23/24-86; d: 12-23/26-86; e: 12-11/12/86;,/! 04-1587; g: 05-26-87; h: 07-10-87; units are: mg per pot. * Chelate-fertilizer was provided by the SCHERING AG. c a t i o n s (Meiwes et al., 1984). M a t r i x b o u n d element c o n t e n t s o f the fine soil were d e t e r m i n e d after a q u a - r e g i a d i g e s t i o n o f g r o u n d s a m p l e s (see Schramel, 1988). Needle

analysis

Needles o f the 1986 a n d 1987 age classes were h a r v e s t e d at intervals before a n d d u r i n g the e x p e r i m e n t f r o m the u p p e r m o s t w h o r l o n each tree. In o r d e r to reduce the b i o m a s s o f tissue r e m o v e d f r o m each tree, samples o f needles f r o m replicate trees within e a c h t r e a t m e n t were p o o l e d p r i o r to n u t r i e n t analysis. A t the final harvest, needle samples f r o m the different age classes o n

234

T. Pfirrmann et al.

each tree were dried at 65°C for 3 days, and then ground and analysed for N, P, S, K, Ca, Mg, AI, Cu, Fe, Mn and Zn (Pfirrmann et al., 1988; Steffen & Schramel, 1988). The final nutrient contents of needles of different age were used to evaluate the proportion of the total nutrients leached from foliage.

Statistical analysis Data which did not exhibit a Gaussian distribution were log-transformed prior to statistical analysis. Data were checked for outliers and then subjected to ANOVA or to t-tests as described elsewhere (Blank et al., 1990).

RESULTS

Soil analysis Soil, texture, water consumption and below ground biomass Dry weights of total pot, coarse and fine soil and below ground biomass are presented in Table 2. The fine soil fraction (important for root growth, water and nutrient uptake) was significantly (P < 0.001) lower in soil 2 compared to soil 1 ( < 1000 and < 1400 g per plant respectively). In addition, there were marked differences between clones in the amount of fine soil and in total pot dry weight, when trees were raised in soil 2. Soil variability between treatments within a given clone and soil type was negligible ( < 2%). There were no differences between treatments on final root dry matter yield (Table 2).

Soit-p/-/ Final analysis of soil pH reflected the chemical status of the different soils. Soil 1, derived from granite, was more acid (pH 4.15 + DE 0-03, n = 96) than soil 2, derived from dolomite (pH 6"88 + SE0"03, n = 96). The variability between pots was < 2%. No treatment or clone-dependent change in soil pH was observed, indicating that sealing the soil surface with a polyethylene lid effectively prohibited acid precipitation from percolating through into the soil. There was no change of soil-pH that might have occurred during irrigation of trees in the nursery during the pre-experimental period. Exchangeable cations Nutrient analysis indicated the principal differences in the chemical composition of the two soils. Soil 1 exhibited significantly (p < 0.001)higher levels of exchangeable A1 and Fe in comparison to soil 2, but lower levels of Ca and Mg (Table 3). Levels of some nutrients did not reflect their original

Mineral and nutrient supply in Norway spruce

235

TABLE 2 Distribution and Proportion of Coarse Soil, Fine Soil and Below-ground Biomass in the Pots of Two Clones (11, 14); units are: g/pot (dry mass)

Clone no.

11

14

Soil

1

2

1

2

Treatment

p H 3 " O pH5"6

pH3"O pH5"6

pH3"O pH5"6

pH3"O pH5"6

Observations Total soil weight Soil > 2 mm diameter Soil < 2 mm diameter Total roots

24

24

24

24

24

24

24

24

2201

2238

1418

1 382

2260

2251

2035

2096

1 275

1 328

865-4

881'5

472'8

1 319 1 336 931"4 13-08 1 4 " 8 3 11'20

445'7

868.1

854.8

924'6 1 383 1 387 745.8 10'21 15.08 1 5 " 8 3 14'06

739.6 13.30

levels in the field as several fertilizer applications had to be made to overcome deficiency symptoms revealed during foliar analyses. One example of this is the level of Mn in soil 2. As Mn availability is often found to be low in this type of soil in the field, the relative availability of Mn in this soil during the experiment may indicate artificially high levels resulting from fertilization. Surprisingly, exchangeable K in soil 2 was significantly (p < 0.001) higher for clone 14 than for clone 11, despite the fact that none of the clones was

4.0 o ~l~ ',~

3.5

2.5 £

2.O

--

1.o

o solid line: control *dashed line: treatment

o

#

"

~- ~,~_ ,,/~"~--~

0.5

2

Fig. 1.

4

6 8 I0 Experimental months

I2

14

16

Mean monthly water supply (mean of all clones and soils per duplicated chamber).

T. Pfirrmann et al.

236

TABLE 3

Results of the NH4C1-Percolates, Units are: meq kg-1 Fine Soil Clone no.

11

14

Soil

1

2

1

2

Treatment

pH 3"O pH 5"6

pH 3"O pH 5"6

pH 3"O pH 5"6

pH 3"O pH 5"6

Observations

12

12

12

12

10

10

12

12

0'37 212 0"58 0"86 98.3 2"76 2'34 316'7

50'9 10.22 2.59 1'38 3.69 1.43 1.83 72"0

47.3 0-47 0.41 11"42 239 258 2-47 0.42 0-46 1"58 3'46 3"48 4.59 93"3 98"1 1.41 1.87 1.99 1.95 3"92 4.32 70'7 342"3 366"7

23"8

27.6

Element

AI Ca Fe K Mg Mn Na CECeff.* (% base saturation

29.0 7.50 3.15 1-01 2.62 1.24 1.55 46.06

28.7 0.69 8.16 223 3.44 0"56 (}93 0"99 3.27 94.0 1.41 2.62 1.83 2.74 47.76 324.7

27.4

29.7

98'8

98'8

99.2

99"2

* Equivalent sum of AI, Ca, Fe, K, Mg, Mn, Na; unit: meq kg- 1 fine soil. fertilized with K. The levels o f exchangeable Ca and Mg in soil 2 were found to be relatively high, carbonate dissolution during percolation probably contributed to these effects. Total exchange capacity and base saturation differed significantly (p < 0.001) between soils, but not between treatments of a particular clone or soil. Marked differences (p < 0-05) were noted in the a m o u n t o f exchangeable A1 in soil 1, when clone 14 was grown in comparison to clone 11 (Table 3). M a t r i x - b o u n d element contents

Available and matrix-bound element fractions were analyzed at the end of the experiment in the fine soil. This indicated the principal differences in the mineral composition o f the two experimental soils (Table 4). D a t a again reflected the fact that fertilizer applications had been made to trees, and indicated that soil chemistry was not identical to that which might be expected in the field. C / N ratios for both soils were relatively low, indicating that conditions were favourable for tree growth and that there was an adequate supply o f soil N. In addition, C / P ratios were rather low for soil 1, reflecting the rather high soil P content through fertilization and the liberation of intrinsic soil pools. No significant effects o f treatment were found on soil nutrient status.

Mineral and nutrient supply in Norway spruce

237

TABLE 4 Results of Elemental Analysis of Two Soils after Aqua regia Digestion in September 1987; units are: g kg-1 fine soil

Clone no.

11

Soil

14

1

2

I

2

Treatment

pH3"O

pH5"6

pH3"O

pH5"6

pH3"O

pH5.6

pH3"O

pH5"6

Observations

12

12

12

12

10

10

I0

12

Element A1 Ct* Ca Fe K Mg Mn N P S C/N C/P

35"77 41-8 0'772 23.91 3"18 3-61 0.334 2.2 1.23 0-34 18.71 34.11

35"55 18"70 18"38 42"0 1 4 4 - 4 144"3 0.798 43.47 44.71 2 3 - 7 9 15.13 14.55 3"19 1.54 1.51 3.66 27.47 28.37 0.345 0-787 0.774 2.3 7.2 7.0 1-27 0-775 0.758 0.343 0.797 0'796 18.13 20.01 20-64 33.44 1 8 6 . 6 190.6

40'38 40-9 0-947 24.03 3-25 3.65 0-385 2.3 1.23 0.351 17.82 33.04

41"25 41"3 0-948 24.92 3"32 3"66 0.414 2"2 1'26 0.354 17.89 33"31

21'32 20"96 181"6 178'2 46.97 46.52 1 2 . 8 4 13.00 3.70 3.79 30.20 29.85 0 . 6 5 1 0-655 9.1 9.1 1.10 1.14 0 " 9 8 6 0-994 19.92 19.55 169.9 160-7

* Ct includes both organic and inorganic carbon originating from dissolved carbonates.

Needle analysis A series of analyses was conducted before, during and at the end of the experiment to evaluate the effects of acid mist and ozone on the foliar nutrient contents of the different clones grown on contrasting soils. At the first harvest in February 1986 (age class 1985), no nutrient deficiencies were observed with the exception of N on soil 2 (Table 5(a)). Further analysis performed in September 1986, which focused on the newly formed needles (age class 1986), revealed severe N deficiency (both soils), Mg (soil 1), Fe and Mn (soil 2) deficiency (see Table 5(b)). Figures 2(a-c) show the changes in selected elements (N, Mg and K) in the 1986 needle year age class for clones 11 and 14 during the course of the experiment. To overcome non-soil specific nutrient deficiencies, trees were fertilized with N, P, Cu, Fe, Mn and Zn (see Table 1). The dose of N applied to soil 1 was enhanced in an attempt to simulate those in the Bavarian forest, where trees exhibit higher N contents than trees in the Calcareous Alps. However, no marked improvement in the N status of trees was achieved (Table 5(c)). Thus, in order to overcome the

Clone

Al

C

Ca

Cu

Fe

K

131 93 108 51

3 394 2840 3970 3 130

2"0 2"8 2"8 10'1

57 51 45 56

12 347 12877 1 675

5-7 4"2 5-5 2'6 8"6 3"8 3"4 3.4

(c) 3rd harvest 21 February 1987, needle age class 1986 n = two trees 5-6 11 1 210 48"1 3 707 1.5 61"6 3"0 I1 1 126 48-0 3242 1"43 43"6 5'6 11 2 12'2 49-3 5015 1-9 11.2

2454 1 920 3 252 1 780 2707 2235 1938 1 940

6 320 4495 5825 4810 7745 7 609 2 642 3 352 7079 7 150 6 625 5487

46-9 43"6 47-5 47-8 46-9 46-7 46"5 46"9

needle age class 1986 n = two trees

48'8 47"3 48"8 47'7 16'4 16"4 16-0 11"9 17.1 8"3 10-8 9"1

(b) 2nd harvest 15 September 1986, 5"6 11 1 93"5 3"0 11 1 69'4 5'6 11 2 71"8 3-0 11 2 48"3 5"6 14 1 36"I 3"0 14 1 30"5 5'6 14 2 5.1 3"0 14 2 3-4

1 2 1 2

harvest 21 February 1986, needle age class 1985 n = two trees

Soil

(a) Preexperimental 11 11 14 14

pH

758 744 2818

685 611 1 101 817 755 758 869 925

800 1 540 911 1 250

Mg

Elements

164 132 20"6

103 49-9 14-0 17-3 88"1 64'4 14.9 11"1

158 36 81 12

Mn

0.44 0'44 1.13

0-50 0.48 1.1 0.76 0.66 0-69 0-61 0.65

1"32 0-79 0"94 0"89

N

1 542 1 186 1 572

1070 1 100 921 827 1 297 1 096 1 182 1 077

1 547 1 368 1 175 1 896

P

909 939 701

655 544 608 545 661 595 528 461

926 917 909 917

S

TABLE 5 Time Course of Element Concentrations in the Needles; Units are: % (C, N);/~g/g ~ (AI, Ca, Cu, Fe, K, Mg, Mn, P, S, Zn)

29"5 27-9 42"2

18'1 16"4 21'8 14'2 20-8 17"2 21"2 18-0

16-8 17"6 24"0 29"0

Zn

oo

11 14 14 14 14

2 1 1 2 2

49.4 93.4 59"5 91.7 17.4

49.3 47.4 47"0 48.4 48-7

1 959 10968 11 476 4895 5 859 8911 8 332 1 500 1 383 8672 9 579 5 843 3 522

1986 n = two f o u r trees 4017 2.9 56.4 3 741 3-4 48-8 6 582 3.0 29.1 6279 3.11 19-1 4060 2.9 51.0 4464 2.8 69-7 3 362 2.3 11.3 3 619 2.6 22-8

1'5 1'9 1-6 n.m. t'4

13"8 30'8 52-6 14"3 13-4

4 074 3 802 4 571 4356 3 599

needle age class 1986 n =.four to sixteen trees 48"4 5 189 3"7 78'5 4538 47"8 5031 3"2 92"3 5487 48"5 10977 3"4 30"7 978 48"6 12436 2"5 23"2 1 112 48"0 5 105 2"9 65"8 4815 48-3 5 004 2"6 55"0 4 924 49-0 6 824 2"6 35"3 2 397 48"7 7 656 3" 1 18"0 2 308

age class 46.9 47-5 47.8 48-1 46.6 46.7 46.8 47.2

(e) Final harvest 15 September 1987, 5"6 11 1 105 3'0 11 1 111 5'6 11 2 14"2 3-0 11 2 12"7 5"6 14 1 72-1 3'0 14 1 69"2 5"6 14 2 10-1 3"0 14 2 9"8

(d) 4th harvest 23 July 1987, needle 5.6 11 1 81.1 3"0 11 1 97-0 5.6 11 2 6"2 3.0 11 2 7'8 5'6 14 1 64'8 3.0 14 1 70'6 5.6 14 2 6"0 3.0 14 2 8-0

3"0 5"6 3"0 5'6 3'0

752 804 4463 4 149 844 813 1 754 2 050

1 278 1 321 3 855 3390 1 101 1 452 1 731 1 924

2 305 758 1 097 1 813 1 899

806 793 35-2 39.0 465 371 10.6 9-1

329 268 61"3 40-8 320 360 12.43 12-0

20" 1 147 185 8'0 8"2

1.51 1.25 1.30 1.35 1-23 1.10 0.99 0.97

1.60 1-51 1.85 1.53 1.44 1.36 !-09 1.12

0"84 0-50 0'54 0'58 0-57

755 792 597 584 786 769 614 565

926 1 013 732 980 1 102 1 514 862 877

1 016 1 174 1 779 1 103 1 301

895 1 255 794 1 154 771 1 266 630 l 024

799 893 790 945 812 1 150 587 767

927 864 1 115 669 929

32"5 40.8 81 6 76-3 31.2 29-3 37.6 35.2

37"9 30"7 61"2 74"1 33"6 45"6 46"5 36"9

46"1 27"2 39"9 35"2 35'8

t,~

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T. Pfirrmann et al.

240

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/ I e / / I

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r

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soil soil soil soil

1 2 1 2

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50 i00 150 200 250 300 350 400 Experimental days: t= 07-i8-1986; 424= 09-14-1987

450

(a)

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50 lO0 150 P00 250 300 350 400 Experimental days: 1= 07-t8-1986; 424= 09-14-1987

450

(b) Fig. 2. T i m e course o f element c o n c e n t r a t i o n in needles; age class 1986. (Harvesting dates: 59, 5 September 1986; 157, 21 J a n u a r y 1987; 354, 7 July 1987; 425, 15 September 1987.)

Mineral and nutrient supply in Norway spruce

241

12

t0

..........

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7~

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lc) Fig.

2--contd.

obvious N deficiency of trees during winter 1986, N fertilization was dramatically increased in spring 1987 and the equivalent of 1000 kg N ha t applied to trees before and during budbreak. Nutrient analyses performed after shoot elongation in July 1987 indicated that this fertilizer regime had been successful and trees no longer exhibited levels of N that might be considered deficient (Table 5(d)) as well as there being no visible symptoms of N deficiency evident. Foliar nutrient contents at the final harvest in 1987 confirmed the improved N status of both needle year age classes (Table 5(e) and Table 6). As a reaction to fertilization of trees with NH4, the availability of K in soil 1 increased (through exchange with K bound in mica). The K content of needles of clones 11 and 14 reflected the expected differences between soils in K supply. At the final harvest, needles of the 1986 age class on trees raised in soil 1 maintained adequate levels of K despite a decline in levels after the development of the current year's needles (1987). In contrast, needles from trees raised on soil 2 exhibited low levels of K (clone 11) and levels that would usually be considered deficient (clone 14). Surprisingly, the K content of needles (1986) of clone 15 raised on the two soils were not significantly different (Table 5). In agreement with field data, foliar Mg and Ca levels were always greater for trees grown on soil 2 compared to soil 1. During the course of the experiment a marked increase in the levels of Ca and Mg was observed in the 1986 needle year age class in trees raised on soil 2, whilst trees raised in soil 1 were low in Ca and Mg throughout (Table 5). Foliar levels of Mg for trees raised in soil 1 were low, but did not reach levels that would be considered deficient. In both needle year age classes levels of P were below threshold values for young spruce trees in the field, even though the

Clone

11 11 11 11 14 14 14 14 15 15 15 15 16 16 16 16 133 133 133 133

pH

5"6 3"0 5-6 3"0 5"6 3-0 5"6 3"0 5"6 3-0 5.6 3"0 5"6 3-0 5.6 3"0 5'6 3"0 5"6 3"0

1 1 2 2 1 1 2 2 1 1 2 2 1 1 2 2 1 1 2 2

Soil

47'4 41"7 6"4 5-9 35'2 34"0 8-1 5"2 49"4 42"0 6"6 4.8 30"8 31"7 5"3 5-6 46"6 44-2 8"6 4.5

AI

47.4 47.2 47-9 48-3 47.9 47.9 47.4 47.8 47.5 48-2 47.7 48"0 47.9 47.6 47-9 47-7 47.3 47-4 47-7 47.7

C

1 135 1 040 1 899 1 928 1 004 1 869 1 845 1 722 1458 1 057 2 525 2 486 1487 1 277 1 881 2786 670 666 2 832 3 091

Ca 3'6 4'3 3"3 3-4 3"1 4' 1 2"8 3"5 5"3 4"2 2"9 2-8 4"3 4"9 3-5 5"6 2-9 3"4 3"6 4-7

Cu 28-7 33"2 14"8 13-0 27"0 27"0 14-1 26"4 34"8 25-1 15-3 14"4 28"4 25"3 13-4 13"6 23'3 20"3 15-7 14"8

Fe 4957 4838 1 867 2 169 3 564 3 481 3 245 3 245 4212 4 120 4281 4 772 3 568 4 332 1 943 2048 3 226 3 767 1 897 2 008

K 445 525 1 481 1 466 396 529 904 958 585 485 1 063 1033 479 597 1 264 1 510 383 398 1 753 1 916

Mg

Elements

628 797 14-0 17"0 318 353 28-7 9"6 722 375 14.7 9-8 737 675 11"1 12'4 128 214 9"9 12"5

Mn 2.12 2-02 1"83 1"38 1'61 1.75 1 14 1.14 2.43 1-90 1-43 1"36 2"65 2-36 1"72 1.82 1.75 1-66 1-89 1-93

N 727 783 813 766 694 740 794 772 911 801 816 778 686 813 704 765 616 677 883 993

P

729 810 654 871 616 788 516 732 816 887 631 796 699 899 625 859 642 614 779 883

S

15"3 16-4 16-6 17-0 15"8 14"9 17-2 17-8 15"8 13.5 18.4 16-8 12.9 12-6 13.2 16-8 11.2 11"7 19"3 18"8

Zn

TABLE 6 Element Concentrations in the Needles at the Final Harvest 15 September 1987, Needle Age class 1987 n = four to sixteen trees. Units are, % (C, N); #g g-~ (Al, Ca, Cu, Fe, K, Mg, Mn, P, S, Zn)

4~

243

Mineral and nutrient supply in Norway spruce availability conditions

of soil-P

was

greater

than

(see s e c t i o n a b o v e h e a d e d

that

found

usually

'Exchangeable

under

field

cations').

The S content of needles exposed to acid mist increased over the course of the experiment,

whilst levels remained

low throughout

control mist. At the final harvest, foliar concentrations were above marked

those that might be considered

differences

between

trees raised

in trees exposed

deficient; however, on

the

to

of all micronutrients

two

there were

soils and

between

different needle year age classes. of soil and mist related changes

in f o l i a r n u t r i e n t

c o n t e n t s o f 1 9 8 6 a n d 1 9 8 7 n e e d l e a g e c l a s s e s is s u m m a r i z e d

Statistical evaluation

f o r all t h e c l o n e s

in T a b l e 7. S i g n i f i c a n t d i f f e r e n c e s i n f o l i a r n u t r i e n t c o n t e n t s b e t w e e n t h e m i s t treatments

i n t h e 1986, b u t n o t i n t h e 1 9 8 7 n e e d l e a g e c l a s s w e r e o b s e r v e d .

TABLE 7 Statistical Evaluation of the Final Needle Analysis for Selected Elements. Mean of all Five Clones Used

Element

Clone

Soil

Treatment

Clone

(mgg- 1 dry weight)

Soil

Treatment

(mg per tree)

1986 Ca

***

***

ns

***

**

Cu

**

**

*

ns

***

***

***

Fe K Mg Mn

*** *** *** ***

*** *** *** ***

** ns ns *

*** *** *** ***

*** *** *** ***

*** * ** ***

N

***

**

***

***

***

***

P

***

***

ns

***

***

**

Zn

***

***

*

***

***

*

*** *** * *** *** *** *** * *

*** ns *** *** *** *** *** * ***

as ns ns ns * ns ns ns *

ns ns ** *** ns *** * ** ***

*** ns *** *** *** *** *** ns ***

ns ns ns ns ns ns ns ns ns

1987 Ca Cu Fe K Mg Mn N P Zn

Significance levels are indicated as: ns not significant. * 0"01 < p < 0 ' 0 5 . ** 0"001 < p < 0 - 0 1 *** p < 0"001.

Mg

K

11

14

11

14

11

Clone

Element

Ca

2

1

Macroelements:

A B C D A B C D A B C D A B C D A B C D

Group

3

1 1 2 2 1 1 2 2 1 1 2 2 1 1 2 2 1 1 2 2

Soil

4

3-0 5.6 3"0 5.6 3-0 5"6 3"0 5-6 3.0 5"6 3"0 5.6 3'0 5"6 3-0 5.6 3.0 5'6 3-0 5'6

pH

5

261-08 104-58 247.67 95'25 284'25 102-00 324-58 102-75 602-75 314.25 200.00 126.50 671-75 4~-42 420-25 294-42 47.92 22-50 118.42 39.42

Total leaching: (Hg per tree, sum of 21 events)

6

46-79 55.67 77.27 53.88 63'87 57"30 67-48 67-15 96-27 99"69 36"80 29-24 83.87 90.58 65.15 81.09 11-73 11"70 37.32 33-08

Needle contents: (age class 1986 + 1987, mg per tree)

7

0"558 0'188 0'321 0"177 0.445 0.178 0'481 0"153 0"626 0"315 0"543 0"433 0-800 0-491 0"645 0"363 0"409 0.192 0'317 0"119

Leaching losses: (percentage of seven)

8 10

2"7

2.1

1-8

1.6

1.3

2'0

3.1

2.5

1.8

3"0

1.3 1.6

1.2 1.4

1.2 0"7

0'9 1.2

1.7 1-1

pH-effect Soil effect on total leaching losses (A:B; C:D) (A:C; B:D)

9

TABLE 8 Leaching Losses from Foliage in 1987 with Respect to the Elemental Contents of the Needle Age classes 1986 Plus 1987

tJ

Zn

Mn

Fe

Microelements:

14

11

14

11

14

11

14

A B C D A B C D A B C D A B C D A B C D A B C D

A B C D

1 1 2 2 1 1 2 2 1 1 2 2 1 1 2 2 1 1 2 2 1 1 2 2

1 1 2 2

3"0 5-6 3"0 5-6 3-0 5"6 3"0 5-6 3"0 5"6 3-0 5-6 3"0 5"6 3-0 5"6 3-0 5"6 3-0 5'6 3"0 5"6 3"0 5"6

3-0 5"6 3.0 5.6

20"15 12-92 18'08 2"83 30"58 7-33 28"92 5-33 55"67 6'17 3'42 0"92 32"50 7"42 3"42 5.42 5"17 2.92 3"75 2"58 4'83 5"83 2'58 2-67

63.42 18.67 101.83 22-92

981"58 995'09 280"47 297"05 775'39 918'87 496"89 411"41 14 375"5 13 017"1 384-50 304-50 7 407"0 7 953.9 202"80 420"90 460-45 465"57 548"21 465"84 417-62 472"45 464-77 444"36

13"28 12.91 25'86 23-37

2'098 1"298 6"450 0'953 3"944 0'798 5-820 1"296 0-387 0.047 0-890 0.300 0"439 0-090 1-686 1.288 1.123 @627 0.684 0.554 1-157 1-234 0-555 0"601

0"478 0"145 0.394 0.098

0"9

0"9

1.2

1.8

1"3

4-9

3-0

2-1 2-1

1.6 1-1

0"3 0-07

2"

=

~.

8.2

0-4 0"2

~e~

~. e~

0-7 0'6

0'3 1-4

1"2 1"5

4"5

4"9

6.8

1"6

4'0

3"3

246

T.

Pfirrmann et al.

However, treatment related differences were due to differences in needle biomass rather than direct effects on foliar concentrations. There were, however, marked differences between clones and between soils in the nutrient content of foliage. Foliar leaching Nutrient analyses of throughfall indicated the response of the above-ground biomass to acid mist and ozone with respect to the accumulated biomass. • ..over

7000 O O

5000

all

limit:

detection

349 /~g/l

OpH 3.0 • pH 5.6

5000 4000 3000

I

o

t '

I O

2000

, • ,,% 1000

i

•

~ - - o , . U/ O , , " ,

, n

50 100 150 Exper'imental days:

/t~o J

~b-o

o

~/~

200 250 300 350 400 ~.= 07-18-~.986; 4;)4= 09-14-t987

450

(a)

1200 i t

i000

00400

i i

o

600

!

!°,,,~o

50

t00

Experimental

/

f.50 days:

0

o o_

200 250 300 350 400 1= 07-18-1986; 424= 09-14-1987

450

(b)

Fig. 3.

Time course of element concentration in throughfiall (clone 1, soil l, vegetation period 1986 plus 1987).

Mineral and nutrient supply in Norway spruce

247

The concentration of Ca and Mg in throughfall for trees of clone 15 grown in soil 1 are presented in Fig. 3. At the beginning of the experiment levels of Ca and Mg in throughfall were extremely high for trees exposed to both mist treatments; however, levels decreased to a minimum, reproducible level after five to six mist events. In spring 1987, after a long period without any mist treatment, losses of Ca and Mg were much less than original levels and within the range found subsequently. The extent of leaching was related to the total nutrient element contents in the 1987 plus 1986 needle year age classes at the end of the experiment (Table 8; Blank et al., 1990). Though leaching of nutrients from foliage was increased by mist o f p H 3'0 compared to pH 5.6, the leached amount expressed as a percentage of the total needle element contents (thus neglecting the possible contribution of older foliage, stems and twigs) was extremely low in both control and acid mist treatments.

DISCUSSION A N D CONCLUSIONS The present study showed clearly that even though acid mist enhanced foliar leaching, the extent of this increase was negligible. It is always difficult to simulate field soil conditions, when long-term experiments involve the intensive growth of plants in relatively small pots. The present experiment suffered to some extent from unsatisfactory sieving and mixing of soils originally collected from the field sites. This reduced much of the effective rootable volume in the pots (Table 2). In addition, inadequate fertilization of trees before and during the early stages of the experiment resulted in foliar levels of some nutrients below threshold values for young Norway spruce trees (Jung & Riehle, 1969; Bergmann, 1986; Hfittl, 1985, 1986). Furthermore, irrigation practices at the nursery, where trees were raised prior to transfer to the chambers, resulted in leaching of nutrients from soil cores, whilst increasing the levels of Ca and Mg Consequently, Ca and Mg availability in soil 1 was much higher than that expected for soils in the Bavarian Forest, which usually exhibit low levels of Ca and Mg, but adequate levels of N, P, K, Mn and Fe (Bosch et al., 1986; Rehfuess, 1986a). In contrast, field conditions in the Alps were more closely simulated by soils 2 (Zech, 1968, 1969; Kruetzer, 1970; Glatzel, 1972; Rehfuess, 1986b, c), with trees exhibiting P, K, Mn and Fe deficiency, but abundant levels of Ca and Mg. The physiological and ecological significance of foliar nutrient leaching has been extensively discussed in the literature (Tukey, 1970; Lovett et al., 1985; Schaefer et al., 1985). Leaching primarily occurs via cation exchange processes, which take place on the surface of leaves and needles (Tukey,

248

T. Pfirrmann et al.

1970), cations are leached from exchangeable pools in the so-called 'apparent free-space' (Epstein, 1972), and the degree of leaching is governed by the particular cation involved, the pH of the leaching medium and the physiological age of the plant tissue (Tukey et al., 1958; Carlisle et al., 1966; Johnson et al., 1985; Lindberg et al., 1986). In addition, the extent of leaching is known to increase with improvements in the nutritional status of tissue (Mahendrappa & Ogden, 1973; Khanna & Ulrich, 1981; Leininger & Winner, 1985). In the present experiment, the net leaching losses from foliage in both mist treatments were extremely low and in neither treatment were effects of sufficient magnitude to cause foliar nutrient deficiency. Losses from foliage were in the same range as those reported in a previous closed chamber experiment conducted by Bosch et al. (1986), and support other reports in the literature that acid mist between pH 2-4 and pH 3.0, in spite of enhancing leaching processes, does not result in foliar nutrient deficiency (Skeffington & Roberts, 1985; Lutz & Breininger, 1986; Kaupenjohann et al., 1988; Mengel et al., 1989). At the beginning of the mist treatments, the levels of elements in throughfall were extremely high, agreeing well with a similar observation made by Mengel et al. (1987). However, we would disagree with their interpretation of these initial losses. Mengel and co-workers suggested that these initial losses reflected destabilization of cell walls and leaching of elements bound to the cell walls; however, as leaching losses in the present experiment remained low following dormancy in spring 1987, it is quite possible that initially high levels of leaching simply reflect washing offofdust and particles from the needle surface. Furthermore, the contribution of cell wall components or intracellular constituents to leaching is equivocable (Mecklenburg et al., 1966). Field studies have demonstrated that the annual turnover of nutrients in canopies of Norway spruce can reach up to 30% of the sorted elements and this increases with the acidity of precipitation. Abrahamsen et al. (1976) showed that treatment of a spruce plantation with acidified water resulted in an increase in throughfall of Mg (67%), K (94%) and Ca (120%), whilst Matzner (1988) found a net turnover of 30% (K, Ca) and 20% (Mg and Mn) of the specific elements in needles during a long-term study with an adult spruce stand in the Solling area. The major problem with these studies is that it is impossible to separate leaching from deposition (Galloway & Parker, 1980; Lindberg et al., 1986). Canopy leaching is often calculated using a model developed by Ulrich and co-workers (Matzner, 1984; Matzner et al., 1984). It cannot be excluded that this model, which compares open-field data with throughfall values, may underestimate the contribution made by dry deposition resulting in overestimation of leaching losses from foliage. Incident precipitation may contribute to a great extent to canopy inputs, yet

Mineral and nutrient supply in Norway spruce

249

it is not represented in the open field data used as the reference for this model. Nihlgard (1970), who conducted a leaching experiment in Southern Sweden simulating the filtering effect of the canopy by using plastic nets, concluded that 70-80% of the Na, Mg, C1 and Ca in throughfall originated from dry deposition. Furthermore, it is now recognized that the dominant process occurring in the canopies of conifers is dry deposition and that measurements made by bulk collectors may grossly underestimate this deposition process. Lindberg et al. (1987) recalculated the Solling data using canopy exchange equations developed in the USA. They found that dry deposition (not directly measured at the Solling site) was 1.6 to 6.0-fold higher than bulk deposition (directly measured). In general, dry deposition appears to supply 10-60% of K, 30-50% of Mg, 20-80% of Ca and 50-60% of Na in net throughfall (Miller et al., 1976; Graustein, 1980). Undoubtedly, leaching losses from old stands are higher than from young seedlings because of the increasing proportion of stems, bark and mature or senescent foliage in field stands. As it is impossible to expose mature trees in climatic chambers, a gap of interpretation will remain. Due to the lack of a complete factorial design we cannot separate mist and ozone effects. Treated and untreated trees did not differ in their mineral contents at the end of exposure; we therefore cannot support the suggestion of an increased loss of foliar minerals by leaching as a reaction to ozone stress. From our results a clear influence of soil and genetic factors upon the nutrition status of Norway spruce is evident. Soil specific nutrient availability, as well as genetically determined nutrient uptake capacity, seem to be of more importance than leaching processes. With respect, however, to the absence of any interaction between plant nutrient status and air pollution (ozone plus acid mist) investigated with very young trees in our long term experiment, we cannot conclude environmentally enhanced leaching losses to contribute to forest decline via increased nutrient deficiencies.

A C K N O W L E D G E M ENTS We are grateful for the reliable assistance of U. Albrecht, M. Roder, J. Schock, K. St~irk, R. Str6bel, I. Roller and W. Kratzl. The continued scientific support ofM. Kloos, Dr C. Bosch, Dr L. W. Blank, Dr H.-D. Payer and Professor K. E. Rehfuess is highly appreciated. We also acknowledge the nursery at Laufen for cultivating the plant material and the Schering AG and BASF AG for providing the fertilizers. Finally, the support of Dr J. D. Barnes for carefully re-reading this paper is kindly acknowledged.

250

7". Pfirrmann et al. REFERENCES

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