499 The concentrations of K, Rb and Cs in spruce needles (Picea abies Karst.) and in the associated soils Armin Wyttenbachl, Sixto Bajol, Jiirg Bucherz, Verena Furrerl, Patrick Schleppil and Leonhard Toblerl 1 Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland Landschaft, CH-8903 Birmensdorf, Switzerland 2 Forschungsanstalt fur Wald, Schnee und Angenommen: 3 1. Marz 1995 - Summary Zusammenfassung nK elemend comnrfationsof K. Rb and Cc were delemined in needles from individual spruce tms as a function of the needle age class. The concentrations am highest in cumnt year's needles and decrease smoothly in older needles, approaching a constant value. Rb and Cs show similar behaviour. whmas that of K differs in so far as its rclative decnasc with lime is less pronounced. Intm- and intersite variation of the needk concentrations 811: largest for Cs and smallest for K. Individual trees show a highly significant conelation between the log (Cs) and log (Rb) values. Total soil concentrations wen determined at 9 sites with different parent material. InIra- and intersite variations of K are compnrahle for soils and for neodlcs. whcrcas those for Rb and Cs arc much smaller for soils than for needles. All the elements arc conelated in soil samples. That is no close connection between soil and needle concentrationsat the various sites. However. the results suggest that needle concentrations of Rb and Cs. but noi of K. are strongly dependent on the sorp(ion propcnies of the associated soils. 1 Introduction The elements K, Rb and Cs are chemically closely related. They arc alkali metals and their ions have many properties in common. For plants, K is an essential major nutritional element, whiie Rb and Cs occur in much smaller amounts and are not essential. The occurrence of K in soils and plants, its uptake from soil into plants and its role in plants are well documented (Scheffer, 1984, Murschncr, 1986). In contrast, such information on Rb and Cs is much more scarce, This is partially due to their nonessential and - when present at natural concentrations - nontoxic nature, but is also an analytical problem. Cs is usually present in plants in very small amounts, and this poses difficulties to most analytical techniques. Z. Pflanzenernahr. Bodenk,, 158,499-504 (1995) Die K-, Rb- und Cs-Konzentrationen in Fichtennadeln (Piceu d i e s Karst) und den dazugehorigen Biiden Die Gchalte der Elemenre K. Rh and Cs wurdcn in Nadeln untcrschiedlichen Alters von einzelnen Fichten gemessen. Die KOn7EIItrah nen sind jewcils am gr(iSten in jungcn Nadeln und nehmen mit zunehmender Nadelalterskliwc sukzcssive bis auf c k n konstantcn Weit ab. Dabei i n das Verhalten von Rh und Cs sehr tlhnlich. w h m d K cine deutlich kleinerc Abnahmc zigt. Die Streuung der Nodclgehalte ist am gr(l6en fUr Cs und tun kinsten fUr K,und &warsowohl zwischcn BUumen auf einem Scpndoit als auch zwkchcn Standurtmittcln.Die Ochalte von Cs und Rb zeigen eine hochsignifikante Komlation ihrer lognrilhmisfhen Weitc. In Bodenprufilen auf 9 Standonen (iiber unterschiedlichem Muttergestein) wurden die Toulgehalte von K, Rb und CYgemessen. D i m Elemcntc sind in Bodenpmben mwohl innerhalb eims Standom ah auch zwischen Standonen kornlien. lhre Sauung in Bodenprobm ist fUr K vergleichbar mil dcrjenigen in Nadeln, wtihnnd sic f i r Rb und Cs in B e n vie1 kleiner als in Nadeln isi. Zwischen den N&l- und Bodengehalten bsteht keine engc Bezichung, Die Ergebnisse deuten jedoch dnrauf hin. da8 die Nadclgehaltc von Rb und Cs,nicht aber diejenigen von K. stark von den A d m o n s c i p e n s c b n der jeweiligcn StandortsWen abhtingen. Information on the radioactive 1 3 T s is much more abundant than on stable Cs. However, a meaningful interpretation of the results of 137Cs in many cases necessitates the knowledge of the data for the stable element. It was the aim of the present work to determine the concentrations of K, Rb and Cs in needles of spruce trees and in the associated soils, and to investigate the relationships existing between the three elements. Since K, Rb and Cs were determined in the same samples, it is certain that they were subject to the same environmental influences. While the variation between plant samples was kept as small as possible by the restriction to Norway spruce and by the separate treatment of the needle age classes, variation between soil data was enhanced by the selection of sites over different parent materials. Due to the rnultielement nature of the 0 VCH Verlagsgesellschaft mbH, D-6945 1 Weinhelm, 1995 0044-3263195fo510-0499 $5.00 + .2S/O 500 analytical technique used, information on many other elements were obtained together with the data for K, Rb and cs. 2 Methods 2.1 Sampling Samples were collected at 9 sites, which will be referred to by their acronyms. Sites were about 100 m x 100 m with an uniform bedrock. From 5 to 9 trees and one or two soil profiles were sampled per site. One site (WIN) differed from the others by its size (12 km x 12 km) and by the greater number of profiles (39) and trees (35) sampled; this site is mostly covered by moraines, but bedrock is not quite as uniform as at the other sites. Trees were sampled by cutting branches from the upper third of the crown in November, taking the 7th whirl if possible. All trees of one site were sampled in the same year. The trees had an age from 50 to 250 years. Twigs were cut from the branches according to the age of their needles, usually collecting age classes 1 to 5. Adhering dust and aerosols were removed by washing with tetrahydrofuran/toluene (Wyttenbach et al., 1992). The twigs were dried, the needles separated from the twig axis and finally ground. Resulting samples contained needles of a given age class from one tree only. Soil samples were taken by horizons down to the subsoil (about 100 cm), dried and sieved (2 mm). An aliquot was then ground and sieved again (0.5 mm). At WIN, sampling was restricted to the topmost 50 cm. 2.2 Elemental analysis K, Rb and Cs along with other elements were determined both in plant and soil samples by instrumental neutron activation analysis (Wyttenbach et al., 1992). Detection limits were 100 pg/g, 100 ng/g and 3 ng/g, respectively. This was sufficient for all samples except for 2 % of the plant samples with Cs. The results for the reference materials NIST-1571 (orchard leaves) and IAEA-Soil-5, which were inserted as control samples at frequent intervals, were in agreement with accepted values. All analytical results are reported with respect to needles dried at 85°C and to soils dried at 65°C. Cleaning the needles prior to analysis is important for samples with low Cs concentrations (< 10 n&), since dust and aerosols on the needle surface would increase these results by about 30 %. Cleaning would not have been necessary for Rb and K. Leaching of endogenous K, Rb and Cs from the needles by the washing procedure is < 0.1 %. 2.3 Abbreviations AC is the needle age class; AC1 denotes needles of the current year, AC2 those sprouted one year before, and so on. The term biodynamic behaviour is used for the change of the concentration in successive ACs, with all ACs sampled at the same date. Variability is expressed as the coefficient of variation (CV) with normal distributions and as the geometric standard deviation (GSD) with other distributions. Wyttenbach, Bajo, Bucher, Furrer, Schleppi and Tobler typical example is given in Fig. 1. This decrease is always found and does not depend on the concentration level, which for Rb and Cs differs by orders of magnitude between sites. The elements Rb and Cs (both for individual trees and for site means) always show a very similar biodynamic behaviour; the ratio Rb/Cs is therefore practically constant for the different ACs. Potassium differs from Rb and Cs at all sites in the manner shown in Fig. 1; owing to these differences, the ratio K/Rb (or K/Cs) is not constant in different ACs, but increases by a factor of 1.7 on average at all sites when going from AC1 to AC3. 25 j Ab 20- 9 \ ?,\ 11 K 1.0- 0.5- 1 2 3 4 nredle age char 5 Figure 1: The biodynamic curves of K, Rb and Cs at site REG. Points are experimental site means (n = 8 trees), curves are given by eq. 1 fitted to the experimental data. Normalization of the concentrations is done such as to give 1 for the mean of all 5 age classes. The normalization value is 473 1 Fg/g for K, 2.8 pg/g for Rb and 13 ng/g for Cs. The ratio K/Rb rises from 1097 in ACI to 2266 in AC 5 at this site. Abbildung 1: Die biodynamischen Kurven von K, Rb und Cs in Fichtennadeln vom Standort REG. Die Punkte sind die Mittelwerte von 8 Baumen, die Kurven wurden durch Anpassung von Gleichung 1 an die experimentellen Daten erhalten. Die Werte jedes Elementes sind so nominiert, dal3 der Mittelwert aller 5 Altersklassen gleich 1 wird. Der Nominierungswert betragt 4731 pg/g fur K, 2.8 pg/g fur Rb und 13 ng/g fur Cs. An diesem Standort nimmt das K/Rb-Verhaltnis von 1097 in Altersklasse 1 bis 2266 in Altersklasse 5 zu. 3.2 Needle concentrations: intra- and intersite variation 3 Results 3.1 Influence of the needle age class The concentrations of K, Rb and Cs depend strongly on the AC, becoming smaller with increasing needle age. A In view of the great influence of the needle age on the concentrations, all subsequent data are given for ACl exclusively. The variation among individual trees within sites is always found to increase as K < Rb < Cs. The mean CV for K is 18 % with little difference between the various K, Rb and Cs in spruce needles Table 1: Site means (a) of K, Rb, Cs in spruce needles (age class 1). Tabelle I: K, Rb und Cs in Fichtennadeln der Altersklasse 1. Mittelwerte der Standorte (a). WIN AUE CHA REG ALP VIL GRO SAR SCH 35 8 8 8 5 6 5 5 9 5298 6387 3974 6595 5216 6733 4944 6061 7655 11.1 2.17 4.60 11.1 5.57 24.0 6.01 24.3 27.8 5.55 384 42.0 513 31.0 647 32.6 19940 146 all sites (n = 9): geometricmean 5780 13.1 GSD 1.22 3.96 477 575 166 27 1 188 17.5 9.6 9.4 .38 2441 1388 713 1097 940 160 159 186 52 194 414 232 247 200 109 60 50 7 440 3.62 109 3.44 sites. Contrary to this the variations of Rb and Cs differ considerably between the various sites (Tobler et al., 1994). At WIN, where more trees were sampled than at other sites, it was found that the distribution of Rb and Cs is lognormal and that of K is normal (Wyttenbach et al., 1991). Mean concentrations for the individud sites are given in Tab. 1. The variation among sites increases again as K < Rb < Cs. The ratio Maxmin for site means is only 1.9 for K, but 67 for Rb and 1800 for Cs. The range for all individual trees is 2750 - 8700 pg/g K, 0.2-194 pgfg Rb and 3 - 28000 ng/g Cs. As a consequence of the different intersite variations for K, Rb and Cs, the ratios K/Rb, Rb/Cs and K/Cs are also very variable. 3.3 Correlations between needle concentrations 119 12.5 48 11.4 (a) Site means are arithmetic for K and geometric for Rb and Cs. (b) Sites are ordered according to the Cs-value. Sites are identified by the first 3 letters of their location: Winterthur ZH, Auenstein AG, Chaneaz VD, Regelsberg SG, Alpthal SZ, Villingen, Grossalp GR, Sardona SG, Schluchsee. All sites are in Switzerland, except VIL and SCH (Black Forest. Germany). Correlations were calculated between the logarithms of the concentrations (AC1) of individual trees from all sites except WIN. This site was excluded in order to avoid an unduly large influence by the great number of trees from this site. Although the correlations between Rb and K (n = 54, r = 0.450) and between Cs and K (r = 0.422) are significant at the 1 % level, the relationships are rather weak, as shown by the low r values. On the other hand, the correla- Table 2: K, Rb and Cs (pg/g) at various soil depths (site WIN) Tabelle 2: K, Rb und Cs (pgjg) in verschiedenen Bodentiefen (Standort WIN) Depth cm horizon 0- 5 5 - 20 20 - 50 Ah Ah, 1 Bv all n cs LO1 (a) K mean cv % Rb mean cv % mean cv % % 37 39 39 13033 13972 14821 18 20 21 82.0 92.6 95.6 18 20 21 5.12 5.20 5.63 23 25 27 16.0 9.5 4.6 115 13958 20 90.2 21 5.32 25 K/Rb Rb/Cs K/Cs 155 195 190 142 I36 150 138 155 94 17.0 23.3 27.0 21.9 13.8 6.0 8.0 13.4 4.2 2642 4545 5135 3 108 1879 893 1101 2086 395 148 1.24 12.7 1.91 1879 2.28 154 167 258 8.8 14.8 1358 2486 (a) Loss on ignition (500"C, 2h) Table 3: K, Rb and Cs (p&) in soils. Site means and comparison with literature data. Tabelle 3: K, Rb and Cs (Iim & Boden. ) Mittelwerte der Standorte und Vergleicb mit Literaturangaben Site bedrock WIN AUE CHA REG ALP VIL GRO moraine moraine moraine molasse flysch red beds (a) moraine (b) quarzite granite SAR SCH soil gleyic Luvisol gleyic Cambisol gleyic Luvisol gleyic Cambisol humic Gleysol dystric Cambisol eutric Cambisol orthic Podzol orthic Podzol this work geometric mean geometric standard deviation Literature data Tibet China USA Illinois (C) (C) (d) (e) a) Buntsandstein b) Derived mostly from limestone n K Rb cs 115 4 5 2 6 3 4 4 2 14'000 15'000 19'000 18'600 18'300 15'300 24'200 33'200 90 77 100 81 137 122 111 156 352 5.3 3.3 3.7 3.7 9.9 20.5 13.9 11.6 84.0 9 17'900 1.37 121 1.59 > 200 > 200 > 200 > 200 20'500 17'900 15'000 133 107 58 89 11'500 c) Tim et al., 1993 d) Shacklette and Boerngen, 1984 9.5 2.85 15.1 7.2 e) Jones, 1989 502 tion between Rb and Cs is very strong (r = 0.976, p < 0.0001): the regression is given by log(Cs) = (- 3.17 k .08) + (1.97 f .06) log(Rb), when the concentrations are in pg/g. It should be noted that the slope of this log-log regression is not unity, meaning that the ratio between Rb and Cs is not constant, but depends strongly on the magnitude of the variables. This latter effect is also seen for the Rb/Cs ratios of the site means (Tab. 1). 3.4 Soil concentrations: influence of soil depth, intraand intersite variation The change of the concentrations with soil depth was evaluated in 39 profiles at WIN (Tab. 2). There is a slight increase for all 3 elements with depth. These changes are completely explained by the dilution of the mineral soil with organic matter near the surface; the same observation was made in profiles at the other sites. Intrasite variation for each of the 3 elements is about 20 %. Mean soil data for all sites (Tab. 3) show considerably larger variations, with intersite variation being smallest for K, intermediate for Rb, and largest for Cs. 3.5 Correlations between soil concentrations At individual sites K, Rb and Cs are always highly correlated. The intrasite correlation at WIN is weakest for Cs-K (n = 115, r = 0.824) and strongest for Rb-K (r = 0.906). The linear regressions have an insignificant intercept, indicating a constant ratio between any two elements in all samples. Site means (Tab. 3, n = 9) also are correlated, with Cs-K (r = 0.859), Rb-K (r = 0.937) and Cs-Rb (r = 0.971). However the significance of these intersite correlations is less, and the scatter of the data larger than for the intrasite correlations. 4 Discussion 4.1 Biodynamics The decrease of the concentrations with needle AC (Fig. 1) is the result of the net translocation of the element from older to younger needles. There is a smooth decrease towards a low, constant value. This behaviour can be described by the function where c(t) is the concentration in AC t (t=l,..S), and A,B, and h are constants. With Rb and Cs it has been shown that neither h nor the ratio B/A vary much among the different sites, whereas A and B show large variations (Tohler et al., 1994). The decrease of the concentrations of K with the age of spruce needles is well documented (e.g. Rademacher et al., 1992), and may also be successfully approximated by eq. 1. Wyttenbuch,Bujo, Bucher, Furrer, Schleppi and Tohler The content of a needle can thus be described as the result of import and export, where the export exceeds the import in each successive AC by an ever decreasing amount, as is reflected in the exponential decrease of the biodynamic curves. In old needles (AC4 and AC5) the export is almost equal to the import since the concentrations no longer change significantly. The export partially satisfies the requirements of the newly formed needles. It is suggested that the compartmentation of K within needle cells (Schmidt et al., 1989) plays a role in these dynamics, different pools having necessarily different mobilities. Dilution effects by increasing needle weights on the biodynamic curves are almost negligible, as may be seen from the fact that needle weight (on average over all sites) increases only by a factor of 1.21 when going from AC 1 to AC4, whereas Rb concentration decreases by a factor of 2.51. The observed decrease also cannot be attributed to foliar leaching since experiments with artificial acid mist and rain failed to show any effect on the concentration of K in needles (Kelly and Strickland, 1986, Pfirrmann et al., 1990). Investigations on the biodynamics of stable Rb and Cs are rare. Robarge et al. (1989) showed that both elements decrease in needles of Picea rubens and Abies fraseri between AC1 and AC3, in agreement with the present findings. Ample evidence, however, is available for the high mobility of 137Cs within the plant. After deposition as radioactive fallout and foliar uptake, 137Cs is efficiently distributed to other plant organs. A similar behaviour is known for R6Rb applied to leaves (Percy and Baker, 1988). The nonessential elements Rb and Cs can be described as approximately following the same biophysical and biochemical processes as the essential K. Because of the similar properties of these ions, they compete in absorption and transport mechanisms, even in the very selective active transport across cell membranes (Rohson and Pitman, 1983). That this competition is not absolute can, however, be seen from our results where Rb and Cs appear more mobile than K, pointing to some differences in their compartmentation or transport. 86Rb is often used as a radioactive tracer for K in plant-physiological studies, but the assumption that Rb behaves exactly like K is brought into question by the present findings as well as by those of Stone and Kszystyniak (1977). For the sake of completeness, it should be added that Na shows a biodynamic behaviour entirely different from its homologues K, Rb and Cs, with concentrations increasing linearly with age. This contrast obviously reflects the physiological discrimination between Na and K, allowing distinct transport and compartmentation (Flowers and Liiuchli, 1983). As a smaller but more hydrated ion, Na can indeed be well separated from K by carriers transporting ions across membranes. On the other hand, biodynamic curves similar to K, Rb and Cs are also observed for other mobile elements such as C1, Cu, Mg, P, and, in some instances, Co, Mn and Zn (Wyttenbach et al., 1995a). 503 K, Rb and Cs in spruce needles 4.2 Concentrations in needles of AC1 4.4 Comparison of needle and soil data Potassium: The values for individual trees at a given site are normally distributed and have a rather narrow range. The different site means to do not vary greatly. The deficiency limit for spruce needles is given as 3500 pg/g (Anonymous, 1986). Since no site mean and only 6 individual trees out of 89 are below this value, poor K availability does not seem a problem in the present investigation. Rubidium and Cesium: One characteristic of Rb and Cs is their lognormal distribution on most sites and their large range, both with individual trees and with site means. Cs has indeed been shown to have the largest variation among all 25 elements investigated in parallel work. Another characteristic of Rb and Cs is their marginal correlation with K, as opposed to the extremely strong, though nonlinear, correlation between Rb and Cs. The pair Rb-Cs has the strongest correlation among the 300 possible combinations from all 25 investigated elements. Paired determinations of Rb and Cs in the same samples are rare. However, it is remarkable that the few values published for various conifers all follow the correlation found for Norway spruce (Wyttenbach et al., 1995b). This correlation therefore seems to be generally valid for conifer needles, irrespective of the species or provenance. The comparison between needle and soil data is made with the assumption that the soil data, normally coming from only one or two profiles per site, are sufficiently representative for the needle data, which come from several trees per site. Since soil data were found to vary considerably less both on a site and between sites than do the needle data, this assumption seems to present no problem. The needle and soil data have some common characteristics, in particular 1) the variation among sites (GSD in Tab. 1 and 3) is largest for Cs and smallest for K. With Cs and Rb, however, this effect is much more pronounced in needles than in soils. 2) The needle data can be grouped roughly into low (WIN, AUE, CHA, REG, ALP), medium (VIL, GRO, SAR) and high (SCH) values, with the grouping being stronger for Cs and Rb than for K. The soil data show approximately the same grouping, but it is much less pronounced. Spearman rank correlation between needles and soil data (n = 9 sites means) is not significant for K (r, = 0.033), but significant for Rb (r, =.700, p < 0.05) and for Cs (rs =.857, p < 0.01). This means that needle concentrations of K are hardly influenced by the total soil concentrations, as it is expected for a selective uptake; Rb and Cs show some connection between the needles and the soil, but since the correlations are nor linear, this connection is not a simple proportionality. On the other hand, needle and soil data differ in various aspects, in particular 1) the close correlation between Rb and K present in the soil is not reflected in the needles, as is evidenced by the much larger variation of K/Rb for needles (GSD 3.44) than for soils (GSD 1.24), and 2) the large range of Rb and Cs and their strong correlation in needles are not shown by the soil. From these differences it is evident that the variation in the total soil concentrations does not sufficiently explain the variation in the needle concentrations. Nevertheless, the extremely strong correlation between the Rb and Cs needle concentrations clearly suggests that a common factor is responsible for their covariation. Since the Cs concentration changes by two orders of magnitude when the Rb concentration changes by one order (as is indicated by the slope of 2 of the log-log correlation), it is evident that this common factor acts much more strongly on Cs than on Rb. The comparatively small variation of the K concentrations further indicates that this factor has only a small influence on the uptake of this element. We consider it as unlikely that this factor represents a selective uptake or discrimination of Rb and Cs by the plant with respect to K, but favour the hypothesis of a soil related factor. Various soil properties have been discussed to influence the avaitability of 137Cs from soils. These include pH, organic matter, exchange capacity, clay content and clay composition (Kiihn et al., 1984, and StefSens et al., 1988). Neither the pH nor the organic matter content of the present sites show any correlation with the needle data. Clay content has not been 4.3 Concentrations in soils As might be expected from the average composition of the upper continental crust (K 28200 pg/g, Rb 112 pglg, Cs 3.7 pg/g), all sites show K >> Rb > Cs. Variation among sites is moderate, being smallest for K and largest for Cs. The soil data for K, Rb and Cs seem to be mostly inherited from the parent material as there is no significant variation with depth within the profiles (Tab. 2). The highest values for all 3 elements, but especially for Rb and Cs, are found at SCH. This is in accordance with the known enrichment of Rb and Cs in granites (Mason and Moore, 1982). The lowest values for Rb and Cs are found at sites over fluvioglacial deposits (AUE, CHA, WIN). All sites are well within the range given in literature. Mean values from this work correspond closely to mean soil values from China and Tibet, whereas Rb in soils from the United States is somewhat lower (Tab. 3). At a given site, the ratio between any two elements is more constant than the elemental concentrations themselves as evidenced by the strong intrasite correlations. This is due to the fact that in individual soil samples elemental concentrations are derived mainly from minerals (feldspar and micas) with a constant ratio between the three elements. Comparing the various sites (Tab. 3), it is found that only the ratio K/Rb is reasonably uniform, whereas K/Cs and Rb/Cs show larger variations. The larger intersite variation of K/Cs and Rb/Cs in soils must be related to the different enrichment of Cs during metamorphic processes involved in the formation of the various bedrocks. Wyttenbach, Bajo, Bucher, Furrer, Schleppi and Tobler determined but its influence is probable. Brouwer et al., (1983), Scheffer and Schachtschahel (1984) and Cornell (1993) have shown that certain clay minerals selectively adsorb large monovalent cations, thereby decreasing their concentration in the soil solution, and that this adsorption increases strongly as K < Rb < Cs, the order given by the intersite variability of the needle concentrations in the present investigation. Sites with small Cs and Rb needle concentrations and a large Rb/Cs ratio (WIN, AUE, CHA, REG, ALP) are thus expected to have a high content of clay and strongly adsorbing minerals, sites with intermediate concentrations and ratios (VIL, GRO, SAR) to have a medium content, and the site SCH, where c s and Rb needle concentrations are largest and the Rb/Cs ratio is smallest, to have a small clay content. These expectations are not unreasonable in view of the involved soils. Fluvioglacial deposits, such as those present at WIN, AUE and CHA are known to contain large amounts of the strongly adsorbing minerals illite, biotite and chlorite (Griitter et al., 1990). On the other hand, the sandy soil at SCH is likely to contain collapsed micas that do not easily adsorb Rb and Cs. If the variations of Rb and Cs between sites are due to different clay contents, then the variation between individual trees on a given site, which is much smaller than the intersite variation, must mainly be due to small-scale local variations of the clay content. Some additional minor variation may also arise from differences in the absorption, transportation and storage behaviour of the individual trees. 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