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Plant Soil (2008) 302:213–220 DOI 10.1007/s11104-007-9471-6 REGULAR ARTICLE Clay minerals as a soil potassium reservoir: observation and quantification through X-ray diffraction Pierre Barré & Christophe Montagnier & Claire Chenu & Luc Abbadie & Bruce Velde Received: 2 August 2007 / Accepted: 30 October 2007 / Published online: 22 November 2007 # Springer Science + Business Media B.V. 2007 C. Montagnier Centre de Versailles-Grignon, INRA, Unité expérimentale grandes cultures, route de Saint-Cyr, 78026 Versailles Cedex, France long term fertilization experiment which allowed one to address the following questions: (1) Do fertilization treatments induce some modifications (as seen from X-ray diffraction measurements) on soil 2:1 clay mineralogy? (2) Are soil 2:1 clay mineral modifications related to soil K budget in the different plots? (3) Do fertilizer treatments modify clay Al, Si, Mg, Fe or K elemental content? (4) Are clay mineral modifications related to clay K content modifications? (5) Are clay mineral changes related to clay Al, Si, Mg or Fe content as well as those of K content? Our results showed that K fertilization treatments considered in the context of soil K budget are very significantly related to 2:1 soil clay mineralogy and clay K content. The 2:1 clay mineral modifications observed through X-ray measurements were quantitatively correlated with chemically analyzed clay K content. Clay K content modifications are independent from clay Al, Si, Mg or Fe contents. These results show that the soil chemical environment can modify interlayer site occupations (illite content) which suggests that high level accumulation of potassium can occur without any modification of the clay sheet structure. This study therefore validates the view of 2:1 clay minerals as a K reservoir easily quantifiable through X-ray observations. C. Chenu Laboratoire BioEMCO, UMR 7618, INRA-CNRS-UPMC-INAPG-ENS-ENSCP, INAPG, Bâtiment EGER, 78850 Thiverval Grignon, France Keywords Abiotic/biotic interactions . Clay minerals . Ecosystem functioning . Long term experiment . Potassium cycle . Soil Abstract Potassium (K) is a major element for plant growth. The K+ ions fixed in soil 2:1 clay mineral interlayers contribute to plant K nutrition. Such clay minerals are most often the majority in temperate soils. Field and laboratory observations based on Xray diffraction techniques suggest that 2:1 clay minerals behave as a K reservoir. The present work investigated this idea through data from a replicated Responsible Editor: Thomas B. Kinraide P. Barré (*) : L. Abbadie Laboratoire BioEMCO,UMR 7618, INRA-CNRS-UPMC-INAPG-ENS-ENSCP, Ecology department, Ecole Normale Supérieure, 46 rue d’Ulm, 75230 Paris cedex 05, France e-mail: [email protected] P. Barré : B. Velde UMR 8538, Laboratoire de Géologie, ENS-CNRS, Ecole Normale Supérieure, 24 rue Lhomond, 75231 Paris Cedex 05, France 214 Introduction Potassium (K) is a major element for plant nutrition. Available soil K is a limiting factor in many agricultural systems (e.g. Evans and Sorger 1966; Kilmer et al. 1968; Oosterhuis and Berkowitz 1996) and K fertilizers are broadly used in agriculture all over the world. Potassium availability can also limit primary production in natural ecosystems. Indeed, a review by Tripler et al. (2006) showed that K fertilization increases primary production in forest ecosystems. Soil potassium availability is also involved in many other ecological processes such as the outcome of inter-specific competition (Tilman et al. 1999). Improving the knowledge about mineral K resources is therefore needed for a better understanding of both natural and cultivated ecosystems. Soil 2:1 clay minerals play an important role for soil K availability. Indeed, several studies showed that the presence of such clay minerals, even in subsidiary quantities, increases effective soil K availability (e.g. Arkcoll et al. 1985; Delvaux et al. 1990; Poss et al. 1991). The particular importance of such clay layers relies on their ability to adsorb and release K+ ions from 2:1 clay mineral interlayer sites (e.g. Hinsinger 2002); these adsorption and release phenomenon can occur over a short period (e.g. Jungk and Claassen 1986). Although, the contribution of clay mineral interlayer K to plant nutrition was often considered to be of minor importance, it is now suspected that it might contribute to a significant part if not the majority of the K supply in many soils (Hinsinger 2002; Øgaard and Krogstad 2005; Andrist-Rangel et al. 2006). Observation and quantification of interlayer K dynamics is therefore most likely a key-parameter for understanding the soil K cycle. Potassium ions are usually anhydrous in soil clay mineral interlayer sites. Soil clay mineral layers which contain anhydrous K+ ions have a 1 nm basal spacing and are traditionally called illite or “illite-like” in the present work. One finds discrete illite in soils, i.e. structures which are exclusively composed of anhydrous potassic interlayers, but generally the greatest part of 1 nm layers in soil clays is associated with smectite layers in mixed layer crystallites. These clay mineral populations are called interstratified illite−smectite and are widespread especially in temperate soils (Wilson 1999; Velde 2001). Barré et al. (2007a) have hypothesized that 2:1 soil clay minerals can behave as a huge Plant Soil (2008) 302:213–220 K reservoir whose dynamic could be observed through X-ray diffraction measurements. Based on a compilation of published data, it was suggested that in a K-rich context some 2:1 layers are able to fix K+ ions forming a 1 nm layer and in a K-poor context some of the collapsed layers could release K+ ions and in doing so, reopen as smectite layers. This hypothesis was successfully tested in laboratory experiments (Barré et al. 2007b). It was demonstrated that K adsorption or release on a soil clay fraction dominated by 2:1 clay minerals could be observed and even quantified through X-ray measurements. The aim of the present study is to provide field evidence for this qualitative and quantitative relationship between 2:1 clay mineralogy (illite layer content) and soil K cycle. In the present study we investigated fertilizer effects, based on X-ray observations and chemical analysis of soil clay fractions from a long term P/K fertilization experiment performed in the INRA Grignon station (Yvelines, France). The following questions have been raised: (1) Did fertilization treatments induce some modifications of soil 2:1 clay mineralogy ? (2) Were soil 2:1 clay mineral modifications related to soil K budget? (3) Did fertilization treatments modify clay Al, Si, Mg, Fe or K content? (4) Are the observed, X-ray diffraction clay mineral modifications related to clay K content modifications? (5) Are clay K content modifications related to changes in clay Al, Si, Mg or Fe content? Methods Fertilization treatments Different P and K fertilization treatments were applied on different plots in cropped fields at the Grignon experimental station (Yvelines, France) of the French Institute for Agronomical Research (INRA). No other fertilizers were added during this experiment. The soil is a Luvisol, its ploughed layer having the following characteristics: sand/silt/clay=9/68/23; pH (H20)= 7.8; pHKCl=7.1; organic C=1.4%; N total=0.14%; CaCO3 =3%; CEC=14 cmolc/kg. In the beginning of the experiment in 1959, the field was divided in 20 plots (7 m×15 m). Fifteen of these plots received about 70 kg of P and 70 kg of K per year during 7 years. The five other plots did not Plant Soil (2008) 302:213–220 215 Sampling procedure receive any fertilizer input from 1959 to the present day. These latter plots will be thereafter referred as 0init. In 1966, a new fertilizer treatment was applied. This treatment was stopped in 10 of the 15 plots previously treated until 1978. In five other plots P and K fertilizer treatments were continued. These plots will be thereafter referred as PKinit. The amounts of P and K fertilizer treatments were respectively 100 and 180 kg ha−1 year−1 during this period. In 1979, the plots treated from 1959 to 1965 and not treated from 1966 to 1978 were divided in two parts. A new fertilizer treatment was applied to the 20 smaller plots (3.5×15 m) from 1979 up to the present day. Among the 20 smaller plots, five received 100 kg/ha of P and 200 kg/ha of K each year from 1979, five received only K, five only P and five neither K nor P. These four groups will be thereafter referred respectively as PK, K, P and 0. The treatments were not modified for the 10 largest plots: the five 0init plots received no input and the five PKinit received 100 kg/ha of P and 200 kg/ha of K per year. Figure 1 presents the distribution of the plots in the field and summarizes the quantities of P and K received from the beginning of the experiment. Each treatment was therefore replicated fivefold. Three soil cores (diameter=5 cm; length=20 cm) were sampled near the center of each plot in October 2006. Twenty centimeters corresponds approximately to the plough depth. The three cores were pooled into one sample which was dried at 60°C, sieved at 2 mm and thoroughly homogenised. Clay fractions recovering procedure We used a physical fractionation procedure to recover the soil clay fraction (<2 μm). For each sample, 20 g of soil were shaken with 100 ml of deionized water at 175 rpm on a shaking plate during 16 h. The suspension was then ultrasonified at 100 J/ml, sieved at 200 μm and centrifuged to separate the 0–2 μm fraction. For that purpose, the suspension was centrifuged at 70×g during 9 min allowing sand and silt fractions to sediment. The supernatant containing the clay fraction was poured in a beaker. This procedure was repeated until the supernatant was quite clear. All the supernatant collected for a given soil sample were pooled. A few milliliters of a 0.5 M strontium chloride solution were added to each pooled supernatant to reach a 0.01 M. About three drops of the flocculated clays were poured on a glass slide for oriented X-ray diffraction. The remaining clay fractions were dried at 60°C. Potassium budget in the plots All plots were cropped with the same plants during the experiment. The crop rotation and the mean yields per fertilizer treatments were determined. We estimated the K content of the matter exported by the crops according to the values determined by the French committee for optimized fertilization (COMIFER 2007). For each fertilizer treatment, the mean K budget was calculated by subtracting the K added as fertilizers and the K exported in the crops (mean yields×K content) since 1959. These budgets are reported on Table 1. Fig. 1 Experimental design of the long term fertilization experiment in the INRA Grignon station (Yvelines, France) K PK 0 P 0init 7m PKinit 15 m 0init 0 K PKinit P PK Chemical analysis of the clay fractions Sub-samples of the 30 clay fractions were compacted into 6 mm diameter and 2 mm thick disks using a hand press and mounted on glass slides and were subjected to X-ray fluorescence analysis of major elements under SEM (scanning electron microscope, EDS-X-ray fluorescence analysis) treatment. For details, see Velde (2006). This technique allowed us PKinit 0 P added quantities since 1959 0 P K PK parcels 0init PKinit P K 0 PK K PK 0init 0init PKinit K (kg/ha) P (kg/ha) PKinit 8090 4690 PK 5980 3280 K 5980 580 P 580 3280 0 580 580 0init 0 0 216 Plant Soil (2008) 302:213–220 Table 1 Mean potassium budget for each treatment Fertilization treatments Total K exported (kg/ha) Total K imported (kg/ha) K budget (kg/ha) 0 P K PK 0init PKinit 4,088.3 580 −3,508.31 4,770.6 580 −4,190.6 4,478.4 5,980 1,501.6 5,029.6 5,980 950.4 3,824 0 −3,824 4,597.4 8,090 3,492.6 The K imported corresponds to the K added as fertilizer from 1959 and the K exported corresponds to the K exported in the crops from 1959 to determine Si, Al, Mg, Fe and K contents in the clay fractions. XRD pattern acquisition and decomposition in the 2:1 clay minerals range The oriented preparations were analysed using an Xray diffractometer using Cu Kα radiation. The XRD diffractograms were obtained at 0.05° step intervals for 3 s counting time in the range of 4 to 13° 2θ. The XRD diffractograms, accumulated as intensityposition counts, could be treated numerically using curve decomposition methods given in Lanson (1997) using a four-point smoothing routine of a background subtracted spectrum. The 30 diffractograms were decomposed into five component curves. Peak positions, intensities and width at half height (WHH) were determined for each X-ray pattern. The area of each curve is approximated by multiplying the intensity by WHH. The following clay mineral identification procedure based on the observations of Moore and Reynolds (1997), Righi et al. (1995) and Velde (2001) was used to attribute a clay mineral population to the peaks: 1. Illite was considered as two components of the peaks at near 1 nm, poorly crystallized illite (PCI) and well crystallized illite (WCI). PCI have a greater peak width than WCI (about 0.9° vs 0.4° 2θ using Cu radiation). PCI have 1.03–1.05 nm spacing whereas WCI have a spacing near 1 nm (for details, see Meunier and Velde 2004). 2. Smectite–illite mixed layer minerals have positions ranging from 1.15 to 1.5 nm depending on the proportion of illite and smectite layers. These phases show peak widths of 1.5 to 2° 2θ using Cu radiation. There are generally two illite−smectite mixed layer components in soils which was the case for our samples. The mixed layered phase with the highest spacing was referred as SI (smectite-rich) and the other as IS (illite-rich). Both are disordered mixed layer minerals according to the criteria of Moore and Reynolds (1997). 3. Chlorite or HI (hydroxyl interlayer phases) or soil vermiculite shows 1.42–1.44 nm spacing and has a narrow peak (near 0.3–0.5° 2θ at peak half height using Cu radiation). These minerals were found in subsidiary quantities in our samples. Calculation of X-ray pattern centre of gravity The peak position of an interstratified illite−smectite clay mineral depends on the relative abundance of each type of layer. The higher the illite content is, the smaller the position in nanometers. One can also consider that the relative peak area of a clay mineral population gives an indication on its relative abundance. Therefore, anhydrous K layers in the clay assemblage decrease the centre of gravity position of the X-ray pattern by increasing the relative area of illite peaks and by shifting the position of interstratified peaks towards smaller positions in nanometers. Based on this, the measurements of the centre of gravity position in the 2:1 clay mineral range should be related to the anhydrous K layer content of the whole clay assemblage and may therefore be used as an approximation of relative K content. Further details can be found in Barré et al. (2007b). The centre of gravity (cg) of the X-ray patterns was easily calculated as follows: cg ¼ .X X ai posi ai ai posi area of the peak i (WHH×intensity) position of the peak i Plant Soil (2008) 302:213–220 217 Peak WHH, intensity and position were all determined by the Decomp program (Lanson 1997). We used the positions measured in nanometers rather than in 2θ angle and the cg position will therefore be thereafter given also in nanometers. Figure 2 shows a decomposed X-ray pattern and the measurement of the position of its centre of gravity. of the clay minerals sampled in the 30 plots (F3,26 = 17.61, P=0.0001). We found a significant “fertK” effect (F1,26 =14.25, P<0.001) which indicated that the K fertilization treatment modified soil clay minerals. There is no effect of the P fertilization (F1,26 =0.32, P= 0.57) nor an effect of the interaction between P and K fertilizations (F1,26 =0.02, P=0.90). Figure 3 presents cg positions plotted against the added K quantities. Statistical analysis All analyses were performed with SAS software (version 8.2). We tested with the GLM procedure if the fertilization treatments had an effect on the position of the centre of gravity. The effects of the model were “fertK”, “fertP” and the interaction “fertP×fertK”. We also tested if the K budgets and the position of the centre of gravity are related. Then, we tested if the fertilization treatments had an effect on clay Al, Si, Mg, Fe and K content. The effects of this model were also “fertK”, “fertP” and the interaction “fertP × fertK”. We performed linear regressions between cg and clay K content and between clay K content and clay Al, Si, Mg and Fe contents with the GLM procedure. Are soil 2:1 clay mineral modifications related to soil K budget? We calculated the mean positions of the centre of gravity of the X-ray patterns of the clay minerals for each fertilization treatment as well as the mean K budget. Figure 4 presents the mean position of the centre of gravity plotted against soil K budget. There is a strongly significant linear relationship between the centre of gravity positions and the soil K budget (F1,4 =122.17, P<0.001, R2 =0.97). The higher the K input the lower the position of the centre of gravity and conversely, the higher the K output the higher the position of the centre of gravity indicating a greater presence of non-potassic smectites minerals. Do fertilization treatments modify Al, Si, Mg, Fe or K content of soil clay fraction? Results Do fertilization treatments modify soil clay minerals? The fertilizer treatments very significantly influenced the position of the centre of gravity of the X-ray patterns SI Position: 1.46 nm Relative area: 0.57 HI Position: 1.42 nm Relative area: 0.02 PCI Position: 1.02 nm Relative area: 0.14 IS Position: 1.16 nm Relative area: 0.22 WCI Position: 1 nm Relative area: 0.05 intensity Fig. 2 Decomposed X-ray pattern of a clay fraction from a K parcel. The bold line represents the measured diffractogram. Each curve corresponds to an identified clay mineral population. The cg position was calculated as follow: cg=0.57× 1.46+0.02×1.42+0.22× 1.16+0.14×1.02+0.05×1= 1.31 nm There is no significant effect of the fertilization treatments on clay Al, Si, Mg of Fe contents. The calculated F and P-values were respectively for Al, SI, Mg and Fe: F3,26 =0.10, P=0.96; F3,26 =0.10, P= 0.96; F3,26 =1.03, P=0.39; F3,26 =0.65, P=0.59). At of gravity position * = centre cg = 1.31 nm 4 5 6 * 7 º2θ Cu Kα 8 9 10 218 Plant Soil (2008) 302:213–220 cg position (nm) 1,36 1,34 1,32 1,3 1,28 1,26 2,5 2,7 2,9 3,1 3,3 3,5 clay K content (%) Fig. 3 Relationship between cg position of X-ray patterns and K fertilization. The equation of the linear regression is: Y= −3.94.10−6(±5.1.10−7)×X+1.32(±2.42.10−5) the opposite, there is a significant effect of the fertilizer treatment on the clay K content (F3,26 = 6.37, P=0.002). In particular, there is a significant effect of the K fertilizer on clay K content (F1,26 = 8.54, P=0.007) and neither an effect of the P fertilizer treatment (F1,26 =0.16, P=0.69) nor effect of an interaction (F1,26 =0.1, P=0.74). Are soil clay mineral modifications related to K content of the soil clay fraction? Figure 5 presents the cg position of the X-ray patterns plotted against the measured K content of the clay fraction. There is a strongly significant negative linear relationship between cg positions and K content (F1,28 =59.43, P<0.0001, R2 =0.68). Clay mineral modifications are therefore strongly correlated with the total K content of the clay fraction. It is also interesting to consider the equation of the regression: Y=−0.072 (±0.009) X+1.52 (±0.03). This means that if the clay assemblage is K free the cg position would be 1.52 nm which is exactly the cg position (nm) 1,34 1,32 1,3 1,28 1,26 -6000 -3000 0 3000 K budget (kg/ha) Fig. 4 Relationship between cg position and soil K budget. The equation of the linear regression is: Y=−4.20.10−6(±5.5.10−7)×X+ 1.30(±1.83.10−3) Fig. 5 Relationship between cg position of X-ray patterns and clay K content position of a bi-hydrated (K free) smectite. Moreover, if we consider the cg position of a mica or a pure illite peak (1 nm), the K content of this clay mineral would be 7.21% according to the equation. A 7.21% K content is in the range of the K content for illite minerals (e.g. Newman 1987). Are clay mineral changes related to clay Al, Si, Mg or Fe content as well as those of K content? There is no relationship between Al and K contents (F1,28 =2.11, P=0.16). There is also no relationship between Si, Mg, Fe and K content (F1,28 =1.81, P= 0.19; F1,28 =0.35, P=0.56; F1,28 =0.01, P=0.90). Clay K content modifications are independent from Al, Si, Mg or Fe contents. Discussion The abscissa position of the cg of X-ray patterns decreased significantly with K fertilizer addition. There is also a very significant relationship between the soil K budget and the abscissa position of the cg of X-ray patterns. Our K budgets have been simplified because we did not take into account the aerial K deposition and K leaching by water soil interaction from the plots. However, the order of magnitude of K leaching and K deposition generally considered in temperate agrosystems (about 5–20 kg ha−1 year−1) are significantly smaller than the quantities of K brought as fertilizers or exported in the crops in our study. Moreover, as deposition and leaching have antagonistic effects on the K budget, ignoring both phenomenon reduces the error on K budgets. Though less informative than a complete K budget, we Plant Soil (2008) 302:213–220 therefore consider that our simplified budget is relevant to support our conclusions: the K budgets in the plots are quantitatively related to clay mineral modifications. This observation supports those general conclusions by Tributh et al. (1987) and Velde and Peck (2002) for similar studies. The modifications observed through X-ray measurements are linked to the modifications of total clay K content. This confirms the quantitative relationship under field condition, for a given clay assemblage, between the position of the centre of gravity of X-ray patterns and the measured clay K content observed in a laboratory experiment performed on “simplified” soils (Barré et al. 2007b). Taken together, all these results show that if the K budget was positive the soil clay minerals of the plot became more potassic with anhydrous (1 nm) layers whereas the quantity of anhydrous K layers decreased if the K budget was negative. Indeed, a clay mineral assemblage with a higher anhydrous K interlayer quantity has a higher total K content and at the same time its X-ray pattern has a lower cg position (more layers collapsed to 1 nm). Consequently, the present study provides the first direct demonstration at the field scale, supported by appropriate statistical analysis, that soil 2:1 clay minerals behave as a K reservoir with a capacity to respond to potassium availability. Contrary to the clay K content, the fertilization treatments did not modify Al, Si, Mg or Fe content of the clay fraction. Moreover, clay K content variations are not correlated with the variation of any of these elements. As Al, Si, Mg and Fe are the most abundant cations in the clay mineral sheets, these results suggest that interlayer K fixation or release does not imply that modifications of the major ions inside clay sheets occurred. However, we did not test if the oxydation degree of the Fe cations was modified by the fertilization treatments. If suggested by our study, we therefore cannot claim that interlayer site occupation modifications are independent from layer charge modifications and such a demonstration needs further research. Our data allow an estimation of the order of magnitude of the size of the K reservoir. The mean difference between total K content of the clay fractions of the plots which received the higher quantity of K fertilizer (“PKinit”) and those which did not receive any input (“0init”) is 2,4 g of K per kilogram of clays. If we consider a soil with a density of 1,000 kg/m3 and a 20% clay content, this means that the fertilizer treatments led 219 to a difference of about 1 t of K per hectare in the clay fraction of the 0–20 cm zone. This is much more than the K quantity needed yearly by plants (50 to 80 kg ha−1 year−1 on average (Schlesinger 1991, p159; Hinsinger 2002)). The reservoir could therefore largely supply the whole K plant needs during the growing season and take back the K yearly released as throughfall or during the litter decomposition. It means that the net K flux could be nearly zero for the reservoir at the yearly scale. Moreover, each year, the values of positive or negative K fluxes are small compared to the K quantity in the reservoir. These arguments may explain why such an important mechanism for the K cycle in terrestrial ecosystems has not been documented until now. Indeed, the differences between soil clay mineralogy before and after the growing seasons should be subtle and localized in the vicinity of roots. It means that even if clay mineral modification occurs after the growing season, the difference is not too diluted to be observed in the bulk soil. Moreover, if the annual net flux of K between soil 2:1 clay minerals and the vegetation is nearly zero, even long term experiments would not allow one to observe clay modifications. That is why, drastic K fertilization treatments coupled with the use of numerical X-ray pattern decomposition program were needed to demonstrate that soil 2:1 clay minerals behave as a K reservoir. The kinetics of the filling and emptying of the reservoir in field condition remains nonetheless an open question which needs further investigations. Clay minerals are also involved in the major soil processes such as aggregate formation, soil organic matter adsorption and soil cation exchange capacity all considered to be properties vital to healthy plant growth. Our study showed that clay minerals could be modified within 46 years, i.e. rapidly compared to assumed pedogenetic time scales. In particular, K uptake in the vicinity of roots should strongly modify clay minerals. We must therefore wonder if these modifications have an influence on soil properties influenced by clay minerals. If so, clay mineral modifications should have some consequences for the functioning of the rhizosphere. Such an idea is supported by the study by Li et al. (2004) which showed that the presence of K ions in interlayer sites modifies pesticide sorption on smectite clays. Given that clay minerals can react at the plant life time scale and that they are involved in major soil processes, we suggest that clay mineral analysis should be an 220 important perspective for a better understanding of ecosystem functioning. Conclusion Our data show that soil 2:1 clay minerals behave as a K reservoir. The filling or emptying of this reservoir could be followed efficiently through X-ray measurements of materials formed under field conditions. This reservoir is likely to have a key role for K cycle in soils. The most evident implications are that it could obviously supply short term K plant needs and preserve long term ecosystem productivity by reducing K leaching. Our work also validates the use of the centre of gravity position to qualitatively and quantitatively study clay mineral modifications in soil dominated by illite and mixed layer illite−smectite clay minerals which open many perspectives for soil K cycle understanding from roots to ecosystem scale. Acknowledgments We deeply thank the technical team of the Grignon experimental station which has performed precisely the fertilization protocol since 1959. We also acknowledge Pascal Denoroy from the INRA Bordeaux who contributed to develop the standard mineral contents of cultivated crops and indicated us these values. We also thank François Rassineux of the ERM society for his help for the clay elemental analyses and the Hydrasa laboratory (Université de Poitiers, France) for the use of their X-ray diffractometers. The help of Jacques Mériguet for the field work was also much appreciated. We acknowledge Gérard Lacroix, Elisa Thébault and Céline Hauzy for their helpful comments on the manuscript. References Andrist-Rangel Y, Simonsson M, Andersson S, Oborn I, Hillier S (2006) Mineralogical budgeting of K in soil: a basis for understanding standard measures of reserve K. J Plant Nutr Soil Sci 169:605–615 Arkcoll DB, Goulding KWT, Hughes JC (1985) Traces of 2–1 layer silicate clays in oxisols from Brazil and their significance for potassium nutrition. J Soil Sci 36:13–128 Barré P, Velde B, Abbadie L (2007a) Dynamic role of “illitelike” clay minerals in temperate soils: facts and hypothesis. Biogeochemistry 82:77–88 Barré P, Velde B, Catel N, Abbadie L (2007b) Soil–plant potassium transfer: impact of plant activity on clay minerals as seen from X-ray diffraction. Plant Soil 292:137–146 COMIFER (2007) Teneurs en P, K et Mg des organes végétaux récoltables. Méthode d’établissement et valeurs de référence. Comifer, Paris Delvaux B, Herbillon AJ, Dufey JE, Vielvoye L (1990) Surface properties and clay mineralogy of hydrated halloysitic soil Plant Soil (2008) 302:213–220 clays. 1. Existence of interlayer K+ specific sites. Clay Miner 25:129–139 Evans HJ, Sorger GJ (1966) Role of mineral elements with emphasis on the univalent cations. Annu Rev Plant Physiol 17:47–76 Hinsinger P (2002) Potassium. In: Lal R (ed) Encyclopedia of soil science. Marcel Dekker, Inc., New-York, USA Jungk A, Claassen N (1986) Availability of Phosphate and Potassium as the result of interaction between root and soil in the rhizosphere. J Plant Nutr Soil Sci 149:411–427 Kilmer VJ, Younts SE, Brady NC (eds) (1968) The role of potassium in agriculture. American Society of Agrononomy/Crop Science Society of America/Soil Science Society of America, Madison, WI, USA Lanson B (1997) Decomposition of experimental X-ray diffraction patterns (profile fitting): A convenient way to study clays. Clays Clay Miner 45:132–146 Li H, Teppen BJ, Laird D, Johnston CT, Boyd SA (2004) Geochemical modulation of pesticide sorption on smectite clay. Environ Sci Technol 38:5393–5399 Meunier A, Velde B (2004) Illite. Springer, Berlin, Germany Moore DM, Reynolds RC (1997) X-ray diffraction and the identification of clay minerals, 2nd edn. Oxford University Press, New-York, USA Newman ACD (1987) Chemistry of Clays. Wiley, New-York, USA Øgaard AF, Krogstad T (2005) Release of interlayer K in Norwegian grassland soils. J Plant Nutr Soil Sci 168:80–88 Oosterhuis DM, Berkowitz GA (eds) (1996) Frontiers in potassium nutrition: New Perspectives on the Effects of K on Physiology of Plants. Potash and Phosphorus Institute of Canada (Publ), Norcross, GA, USA Poss R, Fardeau JC, Saragoni H, Quantin P (1991) Potassium release and fixation in ferralsols (oxisols) from southern Togo. J Soil Sci 42:649–660 Righi D, Velde B, Meunier A (1995) Clay stability in clay dominated soil systems. Clay Miner 30:353–364 Schlesinger WH (1991) Biogeochemistry, an analysis of global change. Academic, San Diego, California, USA Tilman EA, Tilman D, Crawley MJ, Johnston AE (1999) Biological weed control via nutrient competition: potassium limitation of dandelions. Ecol Appl 9:103–111 Tributh H, von Boguslawski E, van Lieres A, Steffens D, Mengel K (1987) Effect of K removal by crops on transformation of illitic clay minerals. Soil Sci 143:404–409 Tripler CE, Kaushal SS, Likens GE, Walter MT (2006) Patterns in K dynamics in forest ecosystems. Ecol Lett 9:451–466 Velde B (2001) Clay minerals in the agricultural horizon of loams and silt loams in the central United States. Clay Miner 36:277–294 Velde B (2006) Preliminary study of the heavy metal chemistry of schorre and slikke clay deposits in the Brouage region: concentration of Cd, Sn and As related to P. Cah Biol Mar 47:93–102 Velde B, Peck T (2002) Clay mineral changes in the Morrow Experimental Plots, University of Illinois. Clays Clay Miner 50:364–370 Wilson MJ (1999) The origin and formation of clay minerals in soils: past, present and future perspectives. Clay Miner 34:7–25