343

Comparison of different laboratory methods with lysimetry for soil solution composition experimental and model results
Bernard Ludwig1*, Karl Josef Meiwes2, Partap Khanna3, Renate Gehlen2, Heike Fortmann2 and Ernst E. Hildebrand4
1

Institute of Soil Science and Forest Nutrition, University of Gttingen, Bsgenweg 2, D-37077 Gttingen, Germany Forest Research Institute of Lower Saxony, Grtzelstr. 2, D-37079 Gttingen, Germany 3 CSIRO Forestry and Forest Products, P.O. Box E4008, Kingston ACT 2604, Canberra, Australia 4 Institute of Soil Science and Forest Nutrition, University of Freiburg, Bertholdstr. 17, D-79098 Freiburg, Germany
2

Accepted 10 January 1999

Summary Zusammenfassung
Compositions of soil solution obtained by the following methods were compared with those obtained by lysimetry: centrifugation; 2:1 extracts of air dried (2:1dried) and field moist (2:1moist) samples; saturation extracts; the `equilibrium soil pore solution' method using columns with undisturbed (ESPS) and composited soil (ESPScomp); and a method using pressure. Two soil depths of a Spodic Dystric Cambisol at Solling, Germany, were sampled with 10 to 12 replications. A coupled equilibrium model was used to describe the effect of soil to solution ratio on the solution composition. The model included multiple cation exchange and inorganic complexation, and for the subsoil solubility products of AlOHSO4 and Al(OH)3. Saturation extracts gave similar results as lysimetry and thus may be useful for calculating output fluxes. However, biological transformations (N mineralisation, solubilisation of organic matter) occurred during the preparation of saturation extracts. Composition of soil solutions obtained by either 2:1dried extracts or centrifugation differed greatly from the results of other methods, indicating that these two methods may not be the best means to investigate equilibrium soil solutions. The values of molar ion ratios depended largely on the method used to obtain soil solutions: Ca2+/Al3+ ratios for each depth ranged from less than 0.3 (which suggests that liming is required urgently) to greater than 1 (liming not necessary). Modelling described the effect of soil to solution ratio on element concentrations for the methods pressure, saturation extracts, ESPScomp and 2:1moist extracts qualitatively with a few exceptions. The model suggested that differences in element concentrations using these methods may be mainly due to dilution, cation exchange and solubilisation of sparingly soluble salts, depending on the soil to solution ratio used. Key words: cation exchange / centrifugation / equilibrium model / lysimetry / mineralisation / saturation extract / soil solution

Vergleich verschiedener Methoden zur Gewinnung von Bodenlsungen experimentelle und Modellergebnisse
Die Zusammensetzungen von Bodenlsungen bei Anwendung unterschiedlicher Methoden wurden mit denen von Lysimeterproben verglichen. Die Methoden beinhalteten Zentrifugation, 2:1Extrakte von luftgetrockneten (2:1dried) und feldfrischen (2:1moist) Proben, Sttigungsextrakte, Gleichgewichtsbodenporenlsungen bei Verwendung ungestrter (ESPS) und homogenisierter (ESPScomp) Bodensulen und die Anwendung von Druck. Zwei Bodentiefen eines Spodic Dystric Cambisols aus dem Solling wurden mit 10 bis 12 Wiederholungen beprobt. Ein bodenchemisches Gleichgewichtsmodell wurde verwendet, um den Effekt des Boden/Lsungsverhltnisses auf die Lsungszusammensetzung zu beschreiben. Das Modell beinhaltete multiplen Kationenaustausch und anorganische Komplexierung und fr den Unterboden zustzlich Lslichkeitsprodukte von AlOHSO4 und Al(OH)3. Sttigungsextrakte ergaben hnliche Ergebnisse wie die Lysimetrie. Sie knnten daher ntzlich zur Berechnung von Elementflssen sein. Biologische Umwandlungen (N-Mineralisierung, Mobilisierung organischer Substanz) traten jedoch bei der Equilibrierung auf. Die Zusammensetzungen der Bodenlsungen der Methoden 2:1dried und Zentrifuge waren stark abweichend von denen der brigen Methoden, welches zeigte, da diese Methoden zum Studium von Gleichgewichtsbodenlsungen weniger gut geignet sind. Die Werte molarer Ionenverhltnisse hingen stark von der verwendeten Methode zur Bodenlsungsgewinnung ab: Ca2+/Al3+-Verhltnisse fr beide Tiefenstufen reichten von kleiner 0.3 (welches anzeigt, da Kalkung dringend notwendig ist) bis zu > 1 (Kalkung ist nicht notwendig). Die Modellierung beschrieb den Einflu des Bodenlsungsverhltnisses auf die Elementkonzentrationen fr die Methoden Druck, Sttigungsextrakte, ESPScomp- und 2:1moist-Extrakte qualitativ mit wenigen Ausnahmen. Das Modell schlug vor, da die Unterschiede in Elementkonzentrationen bei Anwendung dieser Methoden hauptschlich auf Verdnnung, Kationenaustausch und Auflsung schwerlslicher Salze in Abhngigkeit des Bodenlsungsverhltnisses zurckzufhren sind.

1 Introduction
Soil solution composition is a key factor determining plant nutrition, solute movement, weathering processes
* Correspondence: Dr. B. Ludwig; E-mail bludwig@gwdg.de
J. Plant Nutr. Soil Sci. (1999), 162, 343351 (1999)

and nutrient cycling. Despite this importance and considerable research, there is no general agreement on the suitable method for obtaining soil solution and on which factors control soil solution composition. Application of lysimetry to study soil solution composition is common and the usefulness and limitations of
1436-8730/99/0306-0343 $17.50+.50/0

 WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999

344 tension and zero-tension lysimetry have been extensively studied (for reviews see Litaor (1988) and Grossman and Udluft (1991)). Zabowski and Ugolini (1990) recommended the application of lysimetry for pedogenic investigations but they found it less suitable for nutrient uptake studies. Commonly used laboratory methods for obtaining soil solution may be classified into three groups: i) methods which attempt to determine soil solution composition without any change of the original (field) soil solution ratio, such as direct centrifugation of the soil (Gillman, 1976), vacuum displacement (Wolt and Graveel, 1986) and pressure application (Heinrichs et al., 1996); ii) methods which involve addition of water to field moist soils such as saturation extracts (Rhoades, 1982) and artificial recycling of solution for obtaining the equilibrium soil pore solution (ESPS) which puts the emphasis on determining soil aggregation effects (Hildebrand, 1994); and iii) more drastic methods which involve drying of soil and addition of water to obtain wide soil solution ratios such as 2:1dried extracts (Meiwes et al., 1984). Comparisons between different methods have already been reported for some cases. For example, solutions obtained by centrifuging a subalpine Spodosol showed a strong seasonal cycle for major elements whereas the lysimeter solutions remained relatively constant throughout the year (Zabowski and Ugolini, 1990). Soil solution from a forest soil obtained by centrifugation differed significantly from solutions obtained by zero-tension lysimetry and it was suggested that leaching losses from the mor layer may be better assessed by zero-tension lysimetry, whereas the centrifuged soil solution may better reflect nutrient availability and steady-state conditions in the soil (Giesler et al., 1996). Significant differences were found between solution compositions obtained by tension and zero-tension lysimeters (Marques et al., 1996). The vacuum displacement method gave similar results to centrifugation for different soils of Tennessee, USA (Wolt and Graveel, 1986). Soil solution composition is determined by a number of factors such as soil storage and equilibration time (Edmeades et al., 1985), bulking of soil samples (Giesler and Lundstrm, 1993), drying (Bartlett and James, 1980), disaggregation (Hildebrand, 1994), soil to solution ratio (Ulrich and Khanna, 1972; Matschonat and Vogt, 1997)

Ludwig, Meiwes, Khanna, Gehlen, Fortmann and Hildebrand

and extraction procedures. Air drying of soils may result in increased pH and soluble amounts of NH4, NO3, Mn (from aerobic soils), K and SO4. Decreases of soluble Fe and Mn (from inundated areas), NH4, NO3, K, Ca and pH were also reported (Etchevers, 1986; Walworth, 1992). At solution to soil ratios of saturation extracts of up to 0.6 to 0.8 L kg1 soil, the cation concentration is determined by salt desorption whereas at higher solution volumes dissolution processes are important (Ulrich and Khanna, 1972). Variation of the centrifugation time between 15 and 240 min caused significant changes in soil solution composition for different subsurface (Bt) horizons of three Ultisols (Walworth, 1992). The main processes involved are cation exchange, mineral dissolution, organic matter complexation, microbial mediated mineralisation and redox reactions. Soil solution composition is the result of many interactive processes leading to complete or partial equilibria among various processes depending upon the factors involved. Because of the complex nature of these processes, there is a need to use an equilibrium model. We compared soil solution compositions obtained by centrifugation, 2:1 extracts of air dried and moist samples, saturation extracts, lysimetry, the `equilibrium soil-pore solution' method and a method using pressure. Our objectives were i) to find out which factors have a major effect on soil solution composition, ii) to model the effect of the soil solution ratio on element concentrations and iii) to assess the ecological significance of the results obtained by these methods.

2 Materials and methods

2.1 Soils
Soil samples were collected in November 1991 from two depths (515 cm and 3545 cm) of a Spodic Dystric Cambisol (FAO) in Solling, Germany. Samples were taken from twelve locations at the B1 (beech forest) site, each from the south-facing side of a tree in the outer third of its crown projection. The soil at this site has developed in a sandstone/ loess material. Site and stand characteristics were provided by Ellenberg et al. (1986). Relevant characteristics of the soil are shown in Tab. 1. Exchangeable cations were extracted by slowly leaching 2.5 g of air dried soil with 100 mL of 1 mol (NH4Cl) L1. Extractable H+ was obtained from the decrease in pH of NH4Cl after accounting for H+ released on hydrolysis of extractable Al3+ and Fe2+ (Meiwes et al., 1984). Exchangeable Fe was interpreted as Fe2+.

Table 1: Some common soil characteristics. SE of mean in parentheses (n = 12). Tabelle 1: Einige Bodencharakteristika. Standardfehler des Mittelwertes in Klammern (n = 12). Depth (cm) 515 3545 C (%) 3.4 (0.2) 1.0 (0.1) N (%) 0.2 (0.0) 0.1 (0.0) pHCaCl2 pHH2O Total 3.4 (0.0) 4.0 (0.0) 4.1 (0.0) 4.5 (0.0) 123.9 (5.9) 65.8 (2.6) H 6.9 (1.4) 0.0 (0.0) Na 0.2 (0.0) 0.2 (0.1) Extractable cations (mmolc kg1) K Mg 2.1 (0.1) 1.2 (0.1) 1.3 (0.1) 0.5 (0.0)

Ca 2.3 (0.6) 1.4 (0.2)

Mn 2.4 (0.2) 0.9 (0.1)

Fe 0.6 (0.1) 0.1 (0.0)

Al 108.1 (3.3) 61.5 (1.9)

Comparison of soil solution composition

345 2.2.8 Equilibrium soil pore solution of composited samples (ESPScomp)

Procedure was the same as described above except that samples were composited and sieved (< 2 mm). After sieving, the fractions < 2 mm and 2 mm were combined again and put into membrane equipment to obtain the same bulk densities for ESPS and ESPScomp.

2.2 Extraction methods 2.2.1 Lysimetry

Soil solution from 10 cm and 40 cm depth was collected with suction lysimeters with a ceramic P80 cup (Staatliche Porzellanmanufaktur, Berlin). Ceramic cups were rinsed with 0.1 N HCl and then with distilled water. Cups were conditioned in the laboratory by sucking soil solution from soil samples from the depths of 10 or 40 cm which were saturated with distilled water. Lysimeter cups were further conditioned in the field for four weeks by discarding soil solution every two weeks. After the conditioning, a suction of 30 kPa (surface soil) and 50 kPa (subsoil) was applied and samples were obtained two days later (15.11.1991).

2.2.9 Replications
The above described methods were applied to the samples from the 12 locations of the beech forest site (n = 12) for each of the two depths. However, for the pressure method the number of replications was ten for each depth. The sampling locations for lysimetry (n = 12) were in a distance of 1 m to each of the profiles.

2.2.2 Pressure method (Heinrichs et al., 1996)

Field moist soil samples were mixed by hand and sieved (2-mm mesh). 150 to 200 g soil was used to obtain soil solution. Applied pressure was approximately 6 MPa. Pressure was applied for 2 weeks at 25 oC. The soil to solution ratio was 2.97 kg L1 for the surface soil and 3.59 kg L1 for the subsoil.

2.3 Analytical procedures and calculations

All soil solutions were filtered through a membrane filter of 0.45 mm pore width. pH-values were determined by a glass electrode. Concentrations of Na, K, Mg, Ca, Mn, Al and Fe (exchangeable cations) were determined by atomic absorption spectroscopy. Concentrations of Na, K, Mg, Ca, Mn, Al, Fe and S in soil solutions were determined by atomic emission spectroscopy. Concentrations of Cl, NH4+, NO3 and Nt (after UV treatment) were determined colorimetrically using the continuous flow colorimeter TRAACS 800 (Knig and Fortmann, 1996) and of nitrogen and carbon by a C/N analyser (Heraeus vario EL). The difference between Nt and the sum of NH4+ and NO3 is presented as Norg. The measured concentration of Fe in solutions was interpreted as Fe2+. Sums of cations and anions and charge balances were calculated using the WAKO program (Prenzel, 1990) with thermodynamic data sets taken from Lindsay (1979) and Baes and Mesmer (1976).

2.2.3 Centrifugation (Gillman, 1976)

Field moist soil samples were mixed and stored in the dark at 4 oC for 2 days. Soil samples (500 g each) were centrifuged by 1950 g for 20 minutes. The soil to solution ratios were 3.11 kg L1 (surface soil) and 3.61 kg L1 (subsoil).

2.2.4 Saturation extract (Rhoades, 1982)

Extracts of field moist and composited soil samples were obtained one day after sampling after making a saturation paste (equilibrium time 18 20 h at 20 oC) and separated using vacuum. The soil solution ratio was 1.74 kg L1 for the surface soil and 1.98 kg L1 for the subsoil.

3 Modelling the effect of the soil solution ratio on element concentrations

3.1 Structure of soil chemical equilibrium model The batch equilibrium model (BEM) used is described in Ludwig et al. (1998). In this study, BEM calculated coupled equilibria among the ions H, Na, K, Mg, Ca, Al, Mn and SO4 considering the law of mass action for inorganic complexes, the dissociation of water and for the carbonic acid system; solubility product equations for Al(OH)3 and AlOHSO4; cation exchange equations; mass balances; the charge balance for the solution phase; and the Davies equation. Homogeneous reactions are listed in Ludwig et al. (1998). For the subsoil, the ion activity product for Al(OH)3 was set to pIAP = 33.2 which is close to the value for natural gibbsite (May et al., 1979). The ion activity product for AlOHSO4 was set to pIAP = 17.9 which is between the values given for jurbanite (pIAP = 17.8; Nordstrom, 1982) and the one which was determined in a longterm study at this site (pIAP = 18.0; Khanna et al., 1987). These salts were not considered for the surface soil, because soil solutions were undersaturated with respect to gibbsite and jurbanite. The partial pressure of CO2 was assumed to be 0.4 hPa. 3.2 Modelling procedure Solution concentrations of the elements obtained by the pressure method at a soil solution ratio of 3.0 (surface soil)

2.2.5 2:1moist extract

After determining the soil moisture content, distilled water was added to the field moist composited soils to obtain a soil solution ratio of 0.5 kg L1. Suspensions were equilibrated for 24 h at 20 oC and separated using vacuum.

2.2.6 2:1dried extract (Meiwes et al., 1984)

Composited soil samples were air dried, sieved with 2-mm mesh and stored in dark at 10 oC for 10 days. Distilled water (0.2 L) was added to 0.1 kg of soil. Suspensions were equilibrated for 24 h at 20 oC and separated using vacuum.

2.2.7 Equilibrium soil pore solution (ESPS) (Hildebrand, 1994)

The principle of extraction in naturally structured soil samples is to establish a quasi equilibrium with a circulating soil solution in a closed system. Undisturbed field moist soil columns (100 cm3) were weighed and put into membrane equipment. Distilled water (0.1 L) was added. The soil to solution ratio was 0.90 kg L1 for the surface soil and 0.88 kg L1 for the subsoil. The temperature was 8 to 10 oC. Soil solution was withdrawn by vacuum through a membrane filter with a suction of 10 to 30 hPa and then automatically pumped to the top of the soil column (macro pores remain air filled). The duration of circulation was 48 h, corresponding to a turnover of the solution between 20 and 40 times depending on the hydraulic conductivity of the soil.

346 or 3.6 (subsoil) kg L1 were used as initial values in the model. The measured values of NH4Cl-extractable cations were taken as the amount of exchangeable cations. For the subsoil, the model considered unlimited amounts of gibbsite and jurbanite in equilibrium with the solution. Addition of water was done in the model stepwise to reach the soil solution ratios of the methods saturation extracts, ESPScomp and 2:1moist extracts. The equilibrium concentrations for these soil solution ratios were then calculated.

Ludwig, Meiwes, Khanna, Gehlen, Fortmann and Hildebrand

4 Results and discussion

4.1 Extractions without addition of water (soils at field capacity or less) 4.1.1 Centrifugation versus lysimetry Up to 120 times more NH4+, 7 times more K (subsoil) and 2 to 4 times more H and Cl were extracted by the

centrifuge method than by the lysimetry method (Tab. 2). Large amounts of Norg and organic carbon were also released during centrifugation (Tab. 3), indicating that high amounts of organically bound material was converted into soluble form (probably due to lysis of microbial biomass or the release of other easily soluble fractions of organic matter). Only low amounts of Mn (3 to 4 times less than the lysimetry values) and Al (4 times less than the lysimetry value in the subsoil) were obtained by centrifugation. This might be due to the large increase in salt concentration which would cause the double layer on the exchange sites to contract, resulting in the transfer of Al and Mn to the innermost part of the double layer. These results are similar to those reported by Zabowski and Ugolini (1990) who observed that throughout a year centrifuge solution concentrations were frequently greater than those of the lysimeter solutions with the exception of Al and Si.

Table 2: pH, sum of cations and anions and charge balance (mmolc L1) and solubilised elements (mmol L1) for the methods which do not involve any change of the original soil solution ratio. SE of mean in parentheses (n = 10 (pressure) or 12). Characters indicate no significant differences (95 %). nd: not determined. Tabelle 2: pH, Summe an Kationen und Anionen und Ladungsbilanz (mmolc L1) und gelste Elemente (mmol L1) fr die Methoden, die keine nderung des ursprnglichen Bodenlsungsverhltnisses beinhalten. Standardfehler des Mittelwertes in Klammern (n = 10 (Druck) oder 12). Buchstaben zeigen nichtsignifikante Unterschiede (95 %) an. nd: nicht bestimmt. Centrifuge pH Sum of cations Sum of anions Charge balance H Na K NH4+ Mg Ca Mn Al Fe SO4 NO3 Cl Pressure Lysimetry Centrifuge Pressure Lysimetry

Surface soil 3.8 4.1a 4.1a * 749 830 566 709 388 386* 363* 121 178 84a 197 95a (26) (13) (12) nd+ 234 140 (9) (9) 51a 77 35a (3) (9) (10) 120 22 1 (6) (3) (1) 45 29a 30a (3) (4) (2) 46a 49a 57a (8) (3) (4) 3 16 9 (1) (2) (1) 68a 48a 63a (7) (8) (7) 20 11a 8a (2) (1) (2) nd+ 174a 124a (29) (7) 111a 82ab 41b (12) (20) (14) 275a 303a 112 (7) (14) (8)

Subsoil 3.8 4.4 4.3 490* 769 509 332* 689 420 158* 80 89 205 39 55 (30) (4) (4) nd+ 333 157 (54) (6) 33 47 5 (2) (7) (1) 114 14 0 (9) (6) (0) 19a 29 20a (2) (3) (2) 39a 33a 31a (5) (3) (2) 8a 2 11a (0) (1) (1) 17 83a 70a (3) (10) (6) 4 0a 0a (1) (0) (0) nd+ 153a 131a (9) (8) 75a 84ab 17b (25) (41) (9) 257a 318a 158 (11) (66) (11)

+ not determined, because the prefilter used for centrifugation released Na2SO4. * with the exception of Na and SO4.

Comparison of soil solution composition Table 3: Norg, Nt (mmol L1) and DOC (mg L1) obtained by different methods. SE of mean in parentheses (n = 10 (pressure) or 12). Characters indicate no significant differences (95 %). nd: not determined. Tabelle 3: Gehalte an Norg, Nt (mmol L1) und DOC (mg L1) bei Anwendung verschiedener Methoden. Standardfehler des Mittelwertes in Klammern (n = 10 (Druck) oder 12). Buchstaben zeigen nichtsignifikante Unterschiede (95 %) an. nd: nicht bestimmt. Norg Centrifuge Pressure ESPS Saturation extract 2:1moist extract 2:1dried extract Lysimetry Centrifuge Pressure ESPS Saturation extract 2:1moist extract 2:1dried extract Lysimetry 313 157 nd 69a 113 295b 57a 248 126b nd 28a 40a 88b 28a
b

347 1973). The increases for Al, Mn and Fe of the surface soil are in the same order of magnitude as reported by Bartlett and James (1980) for a Spodic horizon sample (B2ir) due to air drying. 4.2.2 Saturation extracts versus 2:1 extracts and ESPS In general, saturation extract concentrations were higher than the 2:1moist extract values (dilution effect), but some exceptions were found for the surface soil and subsoil (Tab. 4). A comparison between the results of the saturation extracts and the 2:1dried extracts shows that in the considered soil solution range the effect of air drying has a greater influence on soil solution composition than the dilution effect (Tab. 4). Concentration values obtained by saturation extracts were greater than the ESPS values because of dilution and aggregation effects. Slight exceptions were found for SO4 and Al (subsoil) and NO3 (surface soil, Tab. 4). 4.2.3 Saturation extracts versus lysimetry Element concentrations obtained by lysimetry and saturation extracts were similar for a number of ions. In the surface soil, values differed by the following factors: Mg (0.8), Ca, Al (0.9), K (1.1), Fe, SO4, Cl (1.3), H (2.1), Mn (2.7). However, for NH4+ and NO3 there were larger differences in both depths. For the subsoils, 29 mmol NH4+ L1 and 28 mmol NO3 L1 were obtained by saturation extracts, whereas the lysimeter solutions contained no NH4+ and only 17 mmol NO3 L1. Higher values of NH4+ and NO3 in the saturation extracts of subsoil than in the lysimeter solutions were the result of mineralisation which occurred during the short period of equilibration for obtaining saturation extracts. NH4+ concentrations in saturation extracts were similar in both depths, but NO3 concentrations were exceptionally low in the surface soil (Tab. 4). This may have been the result of a loss of nitrates by denitrification process under higher C conditions. 4.2.4 ESPS versus lysimetry Main components in the solutions for both depths were H, Na, SO4 and Cl when the ESPS method was applied (Tab. 4). This result is similar to the one obtained by lysimetry. For the other elements, however, the concentrations obtained by ESPS were much less when compared to lysimeter results, especially for Ca, K, NO3 and Mg (Tab. 4). Low concentration values for the ESPS method are expected because of the addition of water (dilution factor), but for Ca especially the values were much lower than expected.

Nt (15) (8) (5) (12) (23) (4) (22) (34) (2) (6) (13) (3) Surface 544 261 nd 98a 133b 367 99ab Subsoil 437 224 nd 85b 48a 109b 45a soil (25) (24) (7) (14) (28) (15) (48) (53) (15) (7) (20) (8)

DOC 42 50a 12 66 31 114 18 24 16 3a 39 7 29 4a

a

(2) (4) (1) (5) (2) (10) (2) (2) (1) (0) (3) (0) (6) (1)

4.1.2 Pressure method versus lysimetry Concentrations of dissolved organic carbon (DOC), Cl, NH4+, Na, Mg and K obtained by the pressure method were higher than those obtained by lysimetry (Tab. 2 and 3). However, concentrations of Ca, Al, Fe, SO4 and NO3 showed no significant differences between the two methods. These similarities suggest that solutions obtained by the pressure method may represent lysimeter data better than centrifugation. However, the pressure method should be applied at lower temperatures and for shorter periods to reduce mineralisation processes. 4.2 Extractions with addition of water 4.2.1 2:1dried versus 2:1moist extracts The comparison of the 2:1dried with the 2:1moist extracts showed that air drying of the soil samples resulted in large increases of element concentrations for both depths (Tab. 4). NH4+ increased by 60 (surface soil) or 13 mmol L1 (subsoil). In the subsoil, soluble K increased by a factor of 11, Mn by 9 and Mg by 3. In the surface soil, considerable increases were found for Mn (5-fold), for K and Ca (3fold), and for Mg, Al and Fe (2-fold). The increase in water-soluble cations was accompanied by an increase of DOC by a factor of 4 for both depths. The increase in the DOC concentration can probably be assigned to increased surface acidity of the clay system due to drying, resulting in proton transfers and release of DOC (Mortland and Raman, 1968) and desiccated micro-organisms (Cohen,

348

Ludwig, Meiwes, Khanna, Gehlen, Fortmann and Hildebrand

Table 4: pH, sum of cations and anions and charge balance (mmolc L1) and solubilised elements (mmol L1) for the methods which involve change of the original soil solution ratio. SE of mean in parentheses (n = 12). Characters indicate no significant differences (95 %). Tabelle 4: pH, Summe an Kationen und Anionen und Ladungsbilanz (mmolc L1) und gelste Elemente (mmol L1) fr die Methoden, die eine nderung des ursprnglichen Bodenlsungsverhltnisses beinhalten. Standardfehler des Mittelwertes in Klammern (n = 12). Buchstaben zeigen nichtsignifikante Unterschiede (95 %) an. 2:1moist extract pH Sum of cations Sum of anions Charge balance H Na K NH4+ Mg Ca Mn Al Fe SO4 NO3 Cl 2:1dried extract Saturat. extract ESPS 2:1moist extract 2:1dried extract Saturat. extract ESPS

Surface soil 4.0a 4.0a 3.8 4.0a 489 843 646 361 257 232 118a (14) 126b (7) 23 (3) 0a (0) 14a (0) 19b (1) 10 (1) 43a (2) 16a (1) 102a (4) 20 (3) 45 (4) 395 458 113a (12) 101a (4) 68 (4) 60 (8) 34 (2) 52ab (18) 46 (7) 76 (5) 28 (6) 148b (7) 12a (2) 109 (10) 462 184 175 (19) 107ab (6) 37 (4) 25 (3) 23 (1) 45a (3) 24 (2) 41a (4) 10a (3) 165b (7) 4b (3) 146 (10) 277 84 99a (9) 105a (7) 7 (1) 1a (0) 14a (1) 3 (0) 5 (1) 39a (5) 3 (1) 100a (6) 11ab (2) 74 (5)

Subsoil 4.2a 4.3a 4.2a 4.4 323 540 484 340 263 60 74a (6) 84 (6) 4a (1) 0a (0) 9 (1) 15 (2) 5a (0) 41a (3) 0a (0) 112 (5) 8a (5) 40 (59) 432 108 60a (7) 102 (3) 42 (4) 13 (6) 29 (2) 40a (7) 43 (4) 42a (4) 2 (1) 172a (5) 8a (5) 95a (11) 432 52 72a (8) 152a (4) 11 (1) 29 (3) 20 (2) 40a (4) 8 (1) 35a (5) 0a (0) 146b (6) 28a (15) 124 (8) 413 73 40 (1) 146a (10) 2a (0) 1a (0) 14 (1) 5 (0) 6a (1) 44a (3) 0a (0) 163ab (8) 9a (3) 90a (6)

4.3 Effect of soil solution ratio (experimental and modelled values) The element concentrations for the methods which use composited samples are plotted versus the solution to soil ratio (Figs. 1 and 2). For the surface soil, model results agree satisfactorily with the experimental ones for K, Ca, Mg and Na. The model suggests that changes in soil solution concentrations with increasing addition of water were mainly due to dilution and to a small extent to cation exchange (desorption of monovalent ions, adsorption of biand trivalent ions). The model could not reproduce Mn, Al and pH values, suggesting that these deviations could be due to desorption and buffering by organic substances (Mulder et al., 1989; Mulder and Stein, 1994) and

desorption of Al and Mn organic complexes with increasing solution soil ratio which were not included in the model. For the subsoil, only a qualitative agreement was found between modelled and experimental values. Largest deviations were found for the centrifugation method, indicating that application of centrifugation resulted in a different equilibrium when compared to the other methods. Further large differences between modelled and measured values were noted for K (concentration obtained by pressure was very large) and Ca (concentration obtained bei ESPScomp was exceptionally low). In almost all cases the model overestimated the concentrations of the 2:1moist extracts.

Comparison of soil solution composition

349

Figure 1: Element concentrations and pH as a function of the solution to soil ratio for the surface soil. Values are shown for the methods centrifugation (triangles at 0.3 L kg1), pressure (circles at 0.3 L kg1), saturation extract (squares at 0.6 L kg1), ESPScomp (diamonds at 1.1 L kg1) and 2:1moist extract (stars at 2 L kg1). Standard errors are also given (n = 10 (pressure) or 12). Solid lines show the model results. Abbildung 1: Konzentrationen verschiedener Elemente und pH als Funktion des Lsungs/Boden-Verhltnisses fr den Oberboden. Werte werden gezeigt fr die Methoden Zentrifugation (Dreiecke bei 0.3 L kg1), Druck (Kreise bei 0.3 L kg1), Sttigungsextrakt (Quadrate bei 0.6 L kg1), ESPScomp (Rauten bei 1.1 L kg1) und 2:1moist Extrakte (Sterne bei 2 L kg1). Standardfehler werden ebenfalls gezeigt (n = 10 (Druck) oder 12). Linien zeigen die Modellergebnisse.

Figure 2: Element concentrations and pH as a function of the solution to soil ratio for the subsoil. Values are shown for the methods centrifugation (triangles at 0.3 L kg1), pressure (circles at 0.3 L kg1), saturation extracts (squares at 0.5 L kg1), ESPScomp (diamonds at 1.1 L kg1) and 2:1moist extracts (stars at 2 L kg1). Standard errors are also given (n = 10 (pressure) or 12). Solid lines show the model results. Abbildung 2: Konzentrationen verschiedener Elemente und pH als Funktion des Lsungs/Boden-Verhltnisses fr den Unterboden. Werte werden gezeigt fr die Methoden Zentrifugation (Dreiecke bei 0.3 L kg1), Druck (Kreise bei 0.3 L kg1), Sttigungsextrakt (Quadrate bei 0.5 L kg1), ESPScomp (Rauten bei 1.1 L kg1) und 2:1moist Extrakte (Sterne bei 2 L kg1). Standardfehler werden ebenfalls gezeigt (n = 10 (Druck) oder 12). Linien zeigen die Modellergebnisse.

5 Practical implications
5.1 Equilibrium solutions Use of air dried soil (2:1dried extracts) and centrifugation resulted in different equilibria compared to the other methods (Tab. 2 and 4; Figs. 1 and 2), indicating that these two methods may not be the best means to investigate equilibrium soil solutions. For the other methods which use composited samples (pressure, saturation extracts, ESPScomp, 2:1moist extracts), model results described the effect of different soil solution ratios on element concentrations qualitatively with a few exceptions. This indicates that differences in element

concentrations using various methods may be mainly due to dilution, cation exchange reactions and solubilisation of sparingly soluble salts (if present in the soil), depending on the soil to solution ratio used. 5.2 Output flux Lysimetry is regarded as useful to determine solute movements (e.g. Zabowski and Ugolini, 1990; Grossmann and Udluft, 1991). Lysimetry values were very low in soluble NH4+, Nt and DOC, indicating only small mineralisation processes and solubilisation of organic matter. According to DOC values, ESPS results were

350
Table 5: Molar ion ratios for different methods. Tabelle 5: Molare Ionenverhltnisse bei Anwendung verschiedener Methoden. Centri- Pressure Lysi- Saturat. ESPS 2:1dried fuge metry extract extract Ca2+/Al3+ Ca2+/H+ Ca /Al Ca2+/H+
2+ 3+

Ludwig, Meiwes, Khanna, Gehlen, Fortmann and Hildebrand

Acknowledgements
We thank M. Pohlmann for providing the solutions obtained by pressure application. B. Ludwig received grants from the German Research Council (DFG) and the Foundation for Advancement of the Gifted Physically Handicapped, Liechtenstein.

2:1moist extract 0.55 0.17 0.49 0.21

0.97 0.32 2.49 0.23

0.88 0.50 0.65 0.83

Surface soil 1.33 1.34 0.62 0.26 Subsoil 0.62 1.54 0.55 0.56

0.10 0.03 0.18 0.12

0.85 0.47 1.36 0.67

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close to lysimetry values. However, amounts of K, Mg and Ca obtained by ESPS were much smaller than lysimetry values. Element concentrations obtained by lysimetry and saturation extracts were similar for a number of ions. However, some differences between the results of these methods were found, especially for NH4+ and NO3 (Tab. 2 and 4), suggesting that during preparation of saturation extracts mineralisation (subsoil and surface soil) and denitrification (surface soil) processes occurred. The similarities between the results of these two methods indicate that soil moisture was close to field capacity when lysimeter solutions were obtained, resulting in a solution composition close to equilibrium. The usefulness of saturation extracts to determine output fluxes should be tested further considering different soil types and textures and seasonal effects. 5.3 Ecological parameters The molar ion ratios of Ca2+/Al3+ and Ca2+/H+ have been suggested to be important parameters for root toxicity (Rost-Siebert, 1983; Cronan and Grigal, 1995). Ulrich et al. (1984) gave criteria regarding liming of forest soils depending on the equivalent fractions of exchangeable cations, pH and ion ratios in soil solutions. They suggested that Ca2+/Al3+ ratios of 2:1 extracts indicate the following: a ratio < 0.3 indicates that liming is required urgently and a ratio 1 indicates that liming is not necessary. In our study, application of the different methods gave a wide range of ratios (Tab. 5): soil solutions obtained by centrifugation (subsoil), lysimetry (surface soil), 2:1dried extracts (subsoil) and saturation extracts had Ca2+/Al3+ ratios greater than 1 (no liming necessary); solutions obtained by centrifugation (surface soil), pressure, lysimetry (subsoil), 2:1dried extracts (surface soil), and 2:1moist extracts had ratios between 1 and 0.3 (liming required); and application of the ESPS method gave ratios below 0.3 (urgent need of liming). These differences indicate that the values of molar ion ratios greatly depend on the method used. We suggest that at least two different methods (with the exception of centrifugation or 2:1dried extracts) are applied before the results are used for recommendations concerning liming or estimates of acidity stress.

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