Aviso de isenção de responsabilidade: Este é um PDF gerado por máquina do conteúdo selecionado de nossos produtos.

Essa
funcionalidade é fornecida somente para sua conveniência e não deve nunca substituir o PDF escaneado originalmente. Nem a
Cengage Learning nem suas licenciadas atestam ou garantem de alguma maneira esses PDFs gerados automaticamente. O PDF
é gerado automaticamente "NO FORMATO EM QUE SE ENCONTRA" e "DE ACORDO COM A DISPONIBILIDADE" e não é
mantido em nosso sistema. A CENGAGE LEARNING E SUAS LICENCIADAS ESPECIFICAMENTE SE ISENTAM DE
RESPONSABILIDADE SOBRE QUALQUER GARANTIA EXPRESSA OU IMPLÍCITA, SEM LIMITAÇÕES, INCLUSIVE
GARANTIAS DE DISPONIBILIDADE, PRECISÃO, PONTUALIDADE, COMPLETUDE, LEGALIDADE, COMERCIABILIDADE OU
ADEQUAÇÃO A UM PROPÓSITO ESPECÍFICO. O uso do PDF automático está sujeito a todas as restrições de uso inclusas no
Contrato de Licença e Assinatura da Cengage Learning e/ou nos Gale Academic OneFile Termos e Condições. Ao usar a
funcionalidade de PDF automático, você concorda em renunciar a qualquer alegação contra a Cengage Learning ou suas
licenciadas pelo uso dessa funcionalidade e qualquer resultado derivado desta.

Illite transformation and potassium release upon changes in

composition of the rhizophere soil solution
Autores: Doris Vetterlein, Thomas Kuhn, Klaus Kaiser and Reinhold Jahn
Data: Oct. 2013
De: Plant and Soil(Vol. 371, Issue 1-2)
Editora: Springer
Tipo de documento: Report
Extensão: 6.833 palavras
DOI: http://dx-doi.ez13.periodicos.capes.gov.br/10.1007/s11104-013-1680-6

Resumo:
Aims and background Release of 'non-exchangeable' potassium (K) from interlayers of illite is diffusion-controlled and has been
shown to depend on the solution concentration of K and other cations ([Ca.sup.2+], [Mg.sup.2+],N[H.sub.4.sup.+]).

Methods We analysed changes in soil solution concentrations of K and competing cations in situ at different distances from the root
surface over time and related them to the transformation of illite, as revealed by X-ray diffraction, and chemical measures of
differently bound K.

Results and Conclusions Within 49 and 98 days, respectively, 6.4 and 14.4 % of the illite's total K was released upon contact with the
root system. Mixed layered minerals increased from 33 (0 d) to 35 (49 d) to 40 % (98 d). Release of K from interlayers and the
transformation of illite occurred at soil solution K concentrations close to the threshold of 80 [micro]M suggested earlier.
Concentrations of Ca and Mg increased with decreasing distance from the root surface, promoting the release of K. The
NaB[Ph.sub.4] method supposed to determine 'non-exchangeable' K extracted only 1/3 of the total K from illite.

Keywords Exchangeable K * Non-exchangeable K * Subsoil * Illite * Soil solution * Ca

Texto completo:
Introduction

The mineral-bound fraction constitutes a major portion of the total potassium (K) in soil (Comerford 2005), with the nature of binding
controlling the release rate. Potassium release from phyllosilicates is more important than from feldspars in most soils (Andrist-
Rangel et al. 2006). Consequently, the K release is closely related to soil texture; soils with high clay mineral content can release
about 35-70 kgK [ha.sup.-1] [a.sup.-1] (Simonsson et al. 2007).

Plants directly control water dynamics, weathering, and the chemistry of weathering solutions, especially in topsoils, being biologically
most active and having usually the highest root densities (Hinsinger et al. 2001; Lucas 2001). In agricultural fields, the topsoil is
amended by fertilizer application, which dominates chemical equilibrium, while fertilizer application has little effect on soil chemistry of
subsoils. Here, plant roots might control weathering of soil minerals.

Roots release H+ or OH-, which exchanges for nutrients ([Mg.sup.2+],[Ca.sup.2+], N[H.sub.4.sup.+], [K.sup.+], N[O.sub.3.sup.-],
[Cl.sup.-]), thus, maintaining charge balance. In consequence, pH may be altered by more than 2.5 pH units in the immediate vicinity
of roots (Jaillard et al. 1996). Concentrations of individual ions can be increased or decreased in relation to bulk soil, depending on
the balance of ion transport to the root surface by mass flow and diffusion and the uptake capacity of the root (Hinsinger et al. 2009).

Large differences in soil K concentration between rhizosphere and bulk soil have been reported (Claassen and Jungk 1982;
Hinsinger and Jaillard 1993; Moritsuka et al. 2004). However, there is little information on gradients and temporal changes in solution
concentrations, which can be large (Vetterlein and Jahn 2004a).

Plants can induce release of interlayer ('nonexchangeable') K in the rhizosphere (Springob and Richter, 1998a). The process is
diffusion-controlled and a consequence of K exchanging for other cations, which partly may have a higher hydration energy. That
increases the interlayer distance spacing, causing the illite to transform into vermiculite (Niederbudde and Fischer 1980; Tributh et al.
1987; Wang et al. 2000).

Most studies are based on analysing different K fractions and plant K uptake before and after growth of plants in pots or field
experiments (Norouzi and Khademi 2010; Tributh et al. 1987). A more detailed study of Claassen and Jungk (1982) using radioactive
[sup.43]K isotopes estimated K solution concentrations as low as 2-3 [micro]M close to the root surface. Such small concentrations
can induce K release from interlayers (Springob and Richter 1998b).

Hinsinger and Jaillard (1993) developed a sophisticated but highly artificial system, in which pre-cultured plants forming a root mat
are contacted to a solidified mica-agar suspension immersed in a nutrient solution, which is renewed daily. The nutrient solution
contained adequate supplies of all nutrients for plant growth, except for K and Mg. Soil solution concentrations were extrapolated
from analysing the agar. The experiment showed, that chemical changes in the rhizosphere can cause release of interlayer K from
phlogopite (a biotite-type layer silicate), which thereby transforms into vermiculite at rates increasing with time and decreasing with
distance to the root surface. The threshold K concentration in solution for the transformation of phlogopite to vermiculite was
calculated to be 80 [micro]M K. Hinsinger and Jaillard (1993) suggested that roots induce depletion of K in the rhizosphere, thus
shifting the exchange equilibrium towards release from interlayer.

Moritsuka et al. (2004), growing corn plants for 17 days in a compartment system, found substantial release of non-exchangeable
interlayer K but no decrease in calculated soil solution K concentration below the threshold of 80 [micro]M K known to trigger such a
release. They hypothesized that at high soil solution concentrations of cations such as [Ca.sup.2+], [Mg.sup.2+], and [Na.sup.+]
exchange of interlayer K and subsequent expansion of the interlayer space is also possible.

That assumption is in line with experiments by Evangelou and Lumbanraja (2002) and Lumbanraja and Evangelou (1990). They
analyzed the reversibility of the illitization of vermiculite, which is related to the concentration of the major cations in the soil solution.

Also, exchange of K for N[H.sub.4.sup.+] and vice versa may control the K depletion profiles around roots (Scherer and Ahrens
1996).

In none of the above mentioned studies (Claassen and Jungk 1982; Hinsinger and Jaillard 1993; Moritsuka et al. 2004) soil solution
concentration was measured in situ, thus the actual K concentration in rhizosphere solution during the time course of the experiments
is not known.

Aim of the present study was to overcome the shortcomings of previous studies and to test following hypotheses by analysing
changes in the composition of the in situ soil solution at increasing distances from the root surface and with time.

Hypothesis 1: There is a strong relationship between the K concentration in the rhizosphere soil solution and the release of K from
illite.

Hypothesis 2: The relationship between K concentration in the soil solution and K release from illite is altered by gradients in soil
solution concentrations between bulk soil and root surface of other cations, in particular [Ca.sup.2+] and [Mg.sup.2+].

As root length density and hence uptake is higher in topsoil than in subsoil, the general expectation for the field situation is that illite
increases with soil depth, while vermiculite decreases (Barre et al. 2007). However, most long-term field trials at forest and grassland
sites showed the opposite, likely because of uptake of mineral nutrients at depth and their subsequent release in surface-near soil
layers during decomposition of plant litter (Tice et al. 1996; Jobbagy and Jackson 2001; Barre et al. 2007). Barre et al. (2007) pointed
out that as long as the balance between K translocation and plant uptake is positive, as in many forest and grassland ecosystems,
illite in surface layers gradually increases. Is the balance negative, as shown for a cropping system by Velde and Peck (2002), the '
illite-type minerals decrease in topsoil. The turning point depends not only on the amount of K exported from the system by harvest or
leaching but on root architecture and subsoil accessibility.

The current experiment was aimed at testing the K release from interlayers in a compartment system. The experimental setup
enables in situ, to sample spatially resolved soil solution at increasing distance from the root mat surface. In addition, soil is sampled
at defined distances from the root surface. The temporal change in K, Ca, Mg, and N[H.sub.4.sup.+] concentrations in soil solution
was analysed as related to changes in clay minerals in the layer in immediate contact with the root surface. X-ray diffraction (XRD)
analysis was complemented by chemical extraction of exchangeable (N[H.sub.4] acetate method), non-exchangeable (NaB[Ph.sub.4]
method), and total K (by X-ray fluorescence (XRF)). In addition, we investigated the depth distribution of clay minerals in three
representative profiles at a long-term arable field site, to obtain hints for illite transformation to mixed-layered minerals and finally
vermiculite under field conditions.

Materials and methods

Experimental design

Alfalfa (Medicago sativa L. cv. Planet) at a rate of 0.5 g per pot was grown under controlled conditions (23 [degrees]C day/18
[degrees]C night; 65 % relative humidity; 14 h photoperiod with 350 [micro]mol[m.sup.-2][s.sup.-1]) in boxes with root compartments
(88 x 32 x 100 mm) separated from bulk soil compartments (88x105x100 mm) by a hydrophilic nylon net (Fig. S1, Vetterlein and Jahn
2004b). Alfalfa seeds were surface sterilized for 10 min in 10 % [H.sub.2][O.sub.2] and soaked in 2 mM CaS[O.sub.4] solution for 2 h.
The root mat formed along the nylon net is regarded as the root surface. The system allows for analysing rhizosphere processes at
known distance from the root surface. The soil reaching from the nylon net into the bulk is designated as rhizosphere.
Microtensiometers ([empty set]0 1.3 mm) (Vetterlein et al. 1993) and micro suction cups ([empty set] 1.3 mm, ceramic made from
Kawenit) (Gottlein et al. 1996) were placed horizontally at a spatial resolution of 30 and 6 mm, respectively. The experiment was set
up as a randomized block design with three replicates. Each compartment system was equipped with two microtensiometers and 15
micro suction cups. The compartments were filled with air dried soil (see below) to a bulk density of 1 g[cm.sup.-3]. No fertilizer was
added.

The packed compartment systems were placed on a sand bed of 5 cm height and moistened by capillary rise to -4 kPa (measured at
40 mm height) by addition of deionised water to the sand bed. Soil moisture was maintained between -4and-6 kPa throughout the
duration of the experiment. At this time all sensors were installed. The first collection of soil solution took place 7 days later, which
corresponds to 0 days after planting (0 d).

We used two treatments; soil only (S) and soil plus a layer of illite (S + I). For the (S + I) treatment, a 1 mm thick perforated
polypropylene plate (holes of 6 mm [empty set]) was filled with illite (2 g per plate) from a mineral deposit (see below). The illite plates
were covered by a 20-[micro]m nylon mesh and inserted between the root compartment and the bulk soil. Three replicates of each
treatment were harvested 49 days (T1) and 98 days after planting (T2). The long cultivation period was chosen as K release from
interlayer and changes in clay mineral assemblage were expected to be slow. To test for possible effects of time, temperature, or
humidity on illite, a (S + I) control without plants was set up in three replicates.

Alfalfa was chosen as test species because of high K requirement. In contrast to many other crop species, shoot size, and thus
transpiration can be controlled by clipping. That allows for maintaining plant size adequate to the size of the compartment system, as
well as for intensive contact between root mat and substrate. Shoots were clipped 35, 49, 70, 84, and 98 days after planting. Dry
matter from each clipping date, root dry matter (49 and 98 days), and K were analysed for calculation of plant K uptake.

Soil

The soil material used for the compartment system experiment comprises the Bt1 and Bt2 horizon of a Haplic Luvisol developed from
loess. It was sampled from 45 to 75 cm depth in an agricultural field in the Lower Rhine Bassin, Germany (Latitude N
50[degrees]37'10", Longitude E 06[degrees]59'41", Elevation 176 ma.s.l.). The site has been used for cropping for more than 100
years, with the last 15 years recorded in detail. Mean soil characteristics are given in Table 1. The soil material was sieved to <2 mm,
and air-dried prior to use.

In addition, three representative soil profiles were selected and sampled by horizons.

Illite

Illite (IMt-2, Cambrianshale, Silver Hill, MT, USA) from a mineral deposit was purchased form Source Clays Repository, The Clay
Minerals Society, Purdue University (http://www.clays.org). Illite was carefully

crushed in a mortar to [less than or equal to] 20 [micro]m particle size.

Soil solution sampling and analysis

Soil solution was sampled simultaneously from all micro suction cups once a week starting at planting (= 0 d). Soil solution was
collected for 3 h towards the end of the night period of the respective day at 30 kPa suction.

Soil solution osmotic potential (cryoscopic measurement Osmomat 300, Gonotec GmbH) and pH (ISFET electrode, IQ240-06 with
PH16SS) were measured on individual soil solution samples. For analyses of Ca, K, Mg, N[H.sub.4.sup.+] and N[O.sub.3.sup.-]
concentrations, samples from each suction cup position of the three replicates of each treatment were combined. Ca, K, Mg were
determined by ICP-OES (Ultima 2, Horiba Jobin-Yvon, Longjumeau, France); and N[H.sub.4.sup.+] and N[O.sub.3.sup.-] using an
automatic photometer (continuous flow analyser ([San.sup.++], Skalar Analytical B.V., Breda, The Netherlands)).

Soil and illite analysis

Illite from the (S + I) treatments was collected separately from the 1-mm plate at harvest and dried at 40 [degrees]C. Soil from (S)
treatments was sliced to obtain the layer in immediate contact with the root mat (0-1 mm). Following analysis were carried out:

Exchangeable K was determined by extracting 0.5 g of soil with 10 ml 1 M N[H.sub.4]-acetate solution (pH 7) for 30 min.

Non-exchangeable K was determined using the NaB[Ph.sub.4] method by Cox et al. (1996). The principle of the method is to
precipitate [K.sup.+] in solution by B[Ph.sub.4.sup.-], thus maintaining steep concentration gradients favoring the release of K. Briefly,
0.5 g of soil were reacted with 5 ml of a solution (1.7 M NaCl, 0.01 M EDTA, 0.2 M NaB[Ph.sub.4]) for 7 days. The suspension was
then transferred into 500-ml glass bottles containing 40 ml 0.5 M N[H.sub.4]Cl and 5 ml 1 M Cu[Cl.sub.2]. The N[H.sub.4]Cl solution
(quenching solution) prevents read-sorption of K and reacts with excess B[Ph.sub.4.sup.-]. Boiling for 20 min dissolves the
precipitates. The suspension is then vacuum filtered through membrane filters and stabilized by addition of 3 drops of 6 N HCl. The K
concentration was measured by ICP-OES (Ultima 2).

Total K was determined by wave length-dispersive X-ray fluorescence analysis (WDXRF). Aliquots of the sample powder were diluted
with [Li.sub.2][B.sub.4][O.sub.7] (1 g sample + 7 g [Li.sub.[2.sub.B4][O.sub.7]) to prepare glass discs by fusion at 1,200[degrees]C in
a 95 % platinium-5 % gold crucible for 20 min. The XRF measurements were performed using a WDXRF spectrometer S4 PIONEER
(Bruker-AXS), equipped with a 4 kW-Rh X-ray tube (75 [micro]m Be window), 60 kV generator, and an eight-position crystal changer.
The spectrometer operating conditions were vacuum, 34-mm collimator mask and 0.23 [degrees] collimator in conjunction with the
analysing crystals OVO 55, Ge, LIF 100, and LIF 110.

Clay mineral identification and semi-quantitative analysis

Clay fractions were separated from bulk soil by sedimentation (Atterberg tubes) without any chemical pretreatment for removal of
organic matter and hydrous Fe oxides. Treatment with oxidative reagents such as [H.sub.2][O.sub.2] can damage mineral surfaces
and change the clay composition (e.g., Mikutta et al. 2005). Clay suspensions were separated into two portions and treated either
with 1 M Mg[Cl.sub.2] or 1 M KCl.
Saturation with Mg, followed by salvation with glycerol, and K is common practice to differentiate vermiculite from smectite (Moore
and Reynolds 1997).

Mineral analyzes of bulk soils and clay fractions were carried out by XRD, using a D5005 diffractometer with CuK[alpha] radiation
(([lambda] =1.541 nm, Siemens AG, Karlsruhe, Germany). Data were obtained on random powder mounts (for bulk soils) and
orientated samples (for clay separates) in stepscan mode with a step size of 0.02 [degrees]2[theta], fixed slits, and 8 s counting time.

The mineral composition of the clay fractions was determined by semi-quantitative analysis, using the intensity and 'full width at half
maximum' of the (001) reflections of the phyllosilicates, normalized to that of (101) quartz peak, and the mineral intensity factors
(Kahle et al. 2002) for calculation of the peak area.

Plant analysis

Shoots were clipped during the experiment 35, 70, 84, and at the destructive sampling of compartments 49 and 98 days after
planting. Roots were washed for 5 min in deionised water to remove adhering soil particles. After determination of dry weight (65
[degrees]C for 48 h), the plant material was subjected to digestion with HN[O.sub.3] (150 mg plant material, 1 ml HN[O.sub.3] (65 %),
6 h at 170 [degrees]C) in a pressure unit (Seif Aufschlusstechnik, Unterschleissheim), and K was determined by ICP-OES (Ultima 2).

Statistics

Differences between treatments were tested for differences by one-factorial ANOVA (SPSS, Version 14.0) at P<0.05. Standard errors
are given in all graphs except those based on measurement in bulk samples (K, Ca, Mg in soil solution).

Results

Soil solution concentrations

Variations in the soil solution osmotic potential for each individual suction cup at similar position (right and left hand side of the
compartment but same distance to root surface) and between treatment replicates were small (supplement Fig. S2), and right and left
hand sides of compartments match each other. Analyses of K, Ca, Mg, and N[H.sub.4.sup.+] required combination of solution
sampled by replicate suction cups. Consequently, no statistical measure of variation can be presented; nevertheless, the results on
the osmotic pressure suggest them to be small, too. For clarity, we present the mean for right and left hand side for each suction cup
position in Figs. 1, 2, and S3, S4.

Solution pH was initially 7.2, and then increased to 8.0 during the first 4 weeks, thereafter it ranged between 7.6 and 8.0 (Supplement
Fig. S3). The observed increase is due to small amounts of carbonate being present. There was no clear change in rhizosphere pH at
the root surface but a trend of increasing values (by 0.2 to 0.4 pH units) from the bulk soil to the root surface. Clipping interrupts the
temporal change in pH values.

Solution K concentrations decreased continuously during the first 4 weeks (Fig. 1). However, no clear depletion with decreasing
distance from the root surface was found as observed in experiments with fertilized quartz sand, where release from the soil matrix
could be excluded (Vetterlein and Jahn 2004a).

The larger K concentrations close to the illite layer in the (S + I) treatment at day 0 and 7 reflect exchangeable K in the illite.

The fluctuation in K concentration after 21 days was not expected and was not observed in a similar experiment, where plants were
grown for 49 days without clipping (data not shown).

The K concentrations were close to the threshold level of 80 [micro]M for release of K from phlogopite interlayers suggested by
Hinsinger and Jaillard (1993).

Solution Ca concentrations were two orders of magnitude larger than K concentrations (Fig. 2). The decrease in Ca concentration in
the bulk soil was accompanied by an increase close to the root surface during the first weeks of the experiment. Eventually, Ca was
depleted throughout the whole system. No differences between the two treatments were apparent. Patterns of Mg concentrations
were similar to those of Ca but one order of magnitude smaller (Fig. S4).

Ammonium concentrations were in general small and close to or below detection limit.

Soil K fractions

For the (S) treatment, the lack of a clear depletion in soil solution K close to root surface is reflected by the different K fractions in the
soil material in immediate contact with the root mat (Fig. 3b). No decrease in exchangeable K was found over time in the 0-1mm
layer, despite a plant uptake (Fig. 4) suggesting a decrease in soil K of 27.2 mg[kg.sup.-1] for the first harvest (49 d) and of 37.4
mg[kg.sup.-1] for the second harvest. There was neither a decrease in ' non-exchangeable' K nor in total K. However, the latter
fraction is large and so the expected decrease is in the range of 0.14 to 0.19 %, which is within variability among replicates of 0.8 %.

For the treatment (S + I), the 4 g of illite in direct contact with the root surface showed decreases in exchangeable as well in total K
over time (Fig. 3a). The larger decrease in total than in exchangeable K indicates K release from interlayers. The decrease in illite K
equaled 28 (first harvest) and 43 % (second harvest) of K uptake by plants.

XRD analyses
Release of K from interlayers was confirmed by XRD analysis (Fig. 5). All replicates showed for the indicating the presence of mixed-
layered minerals. Semi quantitative analyses of the XRD patterns suggest an increase in mixed-layered minerals over time from 33 (0
d) to 35 (49 d) to 40 % (98 d). Vermiculite was only detected after 98 days in the order of 1 %. Without plants, no change of XRD
pattern of illite over time was found (Fig. S6).

For the clay fraction isolated from the 0-1mm soil layer of the treatment (S), XRD showed illite to be the dominant clay mineral (28 %),
followed by vermiculite (14 %), and mixed-layered minerals (14 %) (Fig. 6). No change in XRD patterns over the time course of the
experiment could be observed for treatment (S).

Soil profiles

The three representative profiles sampled from the long-term agricultural field (>100 years of use as arable land) show a decrease in
illite with depth and an increase of mixed-layered minerals and vermiculite with depth (Fig. 7).

Evaluation of NaB[Ph.sub.4] method

The NaB[Ph.sub.4] method developed to extract interlayer K (Cox and Joern 1997) extracted only 1/3 of the total K from pure illite,
which is in conflict with the fact that illite has most K in interlayers. The small amounts of feldspar detected in the pure illite cannot
explain this discrepancy. The NaB[Ph.sub.4]-extractable K decreased with time, however, it never matched the decrease in total K.

Discussion

Clipping

Clipping shoots was done to keep plants at a size adequate to that of pots but still having a well developed root mat in contact with
the substrate over an extended period. Sudden changes in pH (Fig. S3) and slightly delayed changes in soil solution concentrations
(Figs. 1, 2, S4) indicated that this procedure affected the system. Likely, the sudden decrease in transpiration (and hence of transport
by convection) as well as the sudden reduction in uptake did affect the ion concentrations at the root surface. So, future experiments
should avoid clipping. Fortunately, the clipping had no major impact on the release of K from illite, which was already apparent at the
first harvest 49 d after planting.

K release from illite

Release of K from illite is assumed to strongly depend on soil solution K concentration. Springob and Richter (1998b) showed for Ca
concentrations in the range of those in our experiment (2-8 mM) that K concentrations below 3.5 [micro]M trigger exponential K
release from inter-layers. They reported release rates of up to 240 [micro]mol K [kg.sup.-1] [d.sup.-1] from soils dominated by
dioctahedral micas (clay content 11.6 %). For the test illite, we found release rates of 2087 to 2624 [micro]mol K [kg.sup.-1] [d.sup.-1].

Also, Claassen and Jungk (1982) found for [sup.43]K-labelled soil a threshold value of 2-3 [micro]MK in rhizosphere soil solution for
the release of non-exchangeable K. However, that extremely small threshold value was deduced by desorption experiment at soil-to-
solution ratio of 1:50, thus, under non-realistic condition.

Hinsinger and Jaillard (1993) found first indication of interlayer expansion, thus release of interlayer K, for phlogopite at a solution
concentration of 80 [micro]M. The K soil solution concentrations derived by Mitsios and Rowell (1987) from their modeling approach
range from 33 to 85 [micro]M for soils of varying clay mineral assemblage; typical concentrations of Ca + Mg were in the range of 16
to 26 mM.

Moritsuka et al. (2004) conducted rhizobox experiments similar to our compartment system experiments. They found a decrease in '
non-exchangeable' soil K (as revealed by repeated extraction into 0.01 M HCl) within 0-1 mm distance from the roots for two soils
and a biotite but not for orthoclase feldspar. They calculated that the K solution concentrations were always >100 [micro]M and
hypothesized that the enrichment of [Ca.sup.2+], [Mg.sup.2+], and [Na.sup.+] in the rhizosphere support the release of interlayer K
despite of high K concentration.

Schneider (1997) showed that increasing Ca concentrations (from 0 up to 100 mM) can cause increasing release of ' non-
exchangeable' K from soil. Also, increasing Ca concentrations causes an increase of the equilibrium K concentration, i.e., the
concentration at which neither sorption nor desorption occurs.

In the (S + I) treatment, we observed large concentrations of Ca and Mg, very small N[H.sub.4] concentrations, and K concentrations
around 80 [micro]M in rhizosphere solution. Hence, K concentrations were close to the threshold concentration suggested by
Hinsinger and Jaillard (1993); in addition, large concentrations of Mg and Ca promoted competition. Our results indicate that low K
concentrations, as suggested by Springob and Richter (1998b) and by Claassen and Jungk (1982), are only required for the release
of interlayer K at small concentrations of other competing cations.

It is possible that the ' true' concentrations of K in the rhizosphere were lower than those found in solutions sampled by the micro
suction cups. As the soil volume from which soil solution is extracted by suction cups is a function of soil water content and time,
sampling volumes of neighboring suction cups may overlap, thus, attenuating concentration gradients. However, if such gradients
become pronounced, they will be detectable as seen for Ca and Mg concentrations (Fig. 2, S4).

Differences between treatments

Despite similar soil solution composition and K uptake in the two treatments, suggesting similar processes, changes in mineral
composition were only detectable for the (S + I) treatment. We assume that to result from several differences in the spatial distribution
of illite and in sample preparation. In the (S + I) treatment, 4 g of pure illite of a particle size of <20 [micro]m were in direct contact
with the root surface. In the (S) treatment, illite constitutes about 28 % of the clay fraction. Since the clay fraction comprises about 28
% of total soil mass (12.8 g of soil in 0-1 mm layer right and left of the root compartment), the total illite content in 0-1 mm layer
amounted to about 1 g, contained within aggregates <2 mm, resulting from sieving the soil, and likely in contact with other K-bearing
minerals, predominantly feldspars. In the (S) treatment, the 0-1 mm layer was obtained by slicing the soil, while for the (S + I)
treatment the layer was separated from bulk soil by a nylon mesh. For XRD analysis, clay fractions had to be isolated in a separate
step for the (S) treatment, which was not necessary for the (S + I) treatment.

Within 49 and 98 days, respectively, 6.4 and 14.4 % of the illite's total K has been released upon direct contact with the root system
in the (S + I) treatment, resulting in partial transformation to mixed layered minerals and vermiculite. The lack in decrease in
exchangeable K in the (S) treatment hints to release of K from other sources, however, from the present experiment the individual
contribution of illite and feldspar cannot be estimated. However, Moritsuka et al. (2004) showed no significant K release from
orthoclase feldspar at pH>6.

Depth distribution of clay minerals in soil--evidence for nutrient uplift theory?

For several decades, the field where the soil material for the compartment system experiment was sampled, has been cropped with a
rotation of cereals and sugar beet, with sugar beets being grown every 3 to 4 years. The K balance for the field is documented in
detail for the last 15 years prior to sampling. Out of these 15 years, the field was cropped for 13 years with the cereal-sugar beet
rotation, and 2 years prior to sampling alfalfa was grown without fertilizer addition. On average, K balance was slightly negative, with
a loss of 14 kgK [ha.sup.-1] year. Despite the negative overall balance, we found a decrease in illite with depth, while vermiculite and
mixed layered minerals increased (Fig. 7). These findings support the nutrient uplift theory (Tice et al. 1996; Jobbagy and Jackson
2001; Barre et al. 2007), i.e., the re-translocation of K from deeper soil layers to the topsoil via plant uptake. Illite is likely one source
for this K re-translocation, resulting in transformation into mixed-layer minerals and vermiculite in the subsoil. In turn, K released
during degradation of plant litter seems to prevent K depletion in topsoil layers and transformation of illite to mixed-layer minerals and
vermiculite.

Suitability of NaB[Ph.sub.4] method for determination on 'non-exchangeable' potassium

The NaB[Ph.sub.4] method was applied as described in Cox et al. (1996), including modifications published later (Cox et al. 1999),
involving the addition of small amounts of 6 M HCl before centrifugation to avoid precipitation of [Cu.sup.2+] with breakdown products
of NaB[Ph.sub.4]. For the illite samples, the method extracted only 32 to 34 % of the total K. Since almost all K in illite is 'non-
exchangeable' the method clearly fails in extracting most ' non-exchangeable' K. The NaB[Ph.sub.4] method was originally developed
by Scott et al. (1960) and applied to illite by Smith and Scott (1966). They found that at maximum 66 % of total K could be extracted
from illite, irrespective of modifications, e.g., varying the exchange cations or their concentrations or the concentration of
NaB[Ph.sub.4]. However, the authors also showed that sonification for 72 h did finally result in 100 % extraction efficiency and
concluded from XRD analyses that the illite was not destroyed by that treatment. The authors did not provide a satisfactory
explanation why part of the K was not extractable without sonification. For other minerals, i.e., muscovite, sonification was not
required to achieve complete extraction.

It was not mentioned by Cox et al. (1996) why the sonification step was skipped, probably due to the risk of altering soil minerals.
Wentworth and Rossi (1972) reported, despite they could not extract all 'non-exchangeable' K from vermiculite, illite, biotite,
phlogopite, and muscovite, a close relationship between the NaB[Ph.sub.4]-extractable K and plant K uptake. For our study this could
not be confirmed. Thus, due to incomplete extraction of interlayer (non-exchangeable) K and the lack of relation of NaB[Ph.sub.4]-
extractable K and K uptake by plants, we cannot support further use of the method.

Conclusion

The spatial arrangement chosen in the (S + I) treatment proofed suitable for the simultaneous measurement of soil solution
concentrations and changes in mineral assemblage by XRD. At soil solution concentrations in equilibrium with unfertilized subsoil
material, 6.4 and 14.4 % of the illite's total K has been released within 49 and 98 days of plant growth, respectively. This release was
accompanied by a shift in the mineral assemblage towards increasing amounts of mixed-layered minerals. Soil solution K
concentrations were close to the threshold level suggested by Hinsinger and Jaillard (1993). In addition, the increase in Ca and Mg
concentrations with decreasing distance from the root surface during the first weeks of the experiment likely support the K release. To
distinguish between the effect of small K and large Ca, Mg concentrations manipulation of initial soil solution composition would be
required.

Field data on changes in mineral assemblage with depth support the nutrient uplift theory but need to be backed up by
chronosequence studies.

Clipping of plants proved unsuitable since inducing sudden changes in transport and sink size, thus, affecting the soil solution
composition.

The NaB[Ph.sub.4] method did only extract 1/3 of the K present in illite and did not correlate with the changes observed with XRF
analyses. This does not support further use of the method for determination of the non-exchangeable K fraction in soils.

Caption: Fig. 1 Changes in soil solution K concentrations with time and increasing distance from the root surface for soil plus illite (S
+ I) (grey bars) and for soil (S) (hatched bars) treatments. Arrows point at dates of clipping shoots. The vertical line indicates the
position of the nylon mesh (= root surface), which is also the position of the illite layer in (S + I) treatments. Bars represent means of
values measured in the right and left bulk soil compartment. The dotted line indicates the 80-[micro]MK threshold concentration
suggested by Hinsinger and Jaillard (1993). R represents positions of suction cups, reaching 3 mm into the root compartment, i.e., at
3 mm distance of the nylon mesh

Caption: Fig. 2 Changes in soil solution Ca concentrations with time and increasing distance from the root surface in soil plus illite (S
+ I) (grey bars) and soil (S) (hatched bars) treatments. Arrows point at dates of clipping shoots. The vertical line indicates the position
of the nylon mesh (= root surface), which is also the position of the illite layer in (S + I) treatments. Bars represent means of values
measured in the right and left bulk soil compartment. R represents positions of suction cups, reaching 3 mm into the root
compartment, i.e., at 3 mm distance of the nylon mesh

Caption: Fig. 3 Changes in exchangeable, 'non-exchangeable', and total K with time in layers of illite or soil in immediate contact (0-1
mm) to the root mat after planting alfalfa. Grey bars refer to illite layers in soil plus illite (S + I) treatments; hatched bars refer to soil
(S) treatments. Exchangeable K was determined using N[H.sub.4] acetate, 'non-exchangeable' by the NaB[Ph.sub.4] method, total by
XRF. Standard errors are given for means but are not always visible due to small size

Caption: Fig. 4 Cumulative K uptake by shoots and roots of alfalfa grown for 49 and 98 days in soil plus illite (S + I) (grey bars) and
soil only (S) (hatched bars) treatments. Standard errors of means of three replicates are given. Cumulative K uptake includes uptake
into shoots clipped on day 35, 70, and 84

Caption: Fig. 5 XRD spectra of the illite layer in individual replicates (I, II, III) of the (S + I) treatment 0, 49, and 98 days after planting

Caption: Fig. 6 XRD spectra of the clay fraction of the 0-1 mm layer of individual replicates (I, II, III) of the (S) treatment 0, 49, and 98
days after planting. Position of basal reflections of illite (dotted line) and vermiculite (dashed line) are shown at 1.0 nm and 1.42 nm d
spacing

Caption: Fig. 7 Depth distribution of mixed layered minerals (light grey), vermiculite (black), illite (white) and kaolinite (dark grey) in
three Haplic Luvisols at Klein-Altendorf, Germany. The area has been cropped with a cereal-sugar beet rotation for the last 15 years
prior to sampling. Values are derived by semi-quantitative analyses of XRD spectra

DOI 10.1007/s11104-013-1680-6

Received: 19 September 2012/Accepted: 6 March 2013/Published online: 22 March 2013

Acknowledgments Andreas Rammler and Jutta Frohlich conducted the XRF analyses. Christine Krenkewitz and Tina Truszezinski
carried out clay fractionation, chemical extractions, and analyses of plant, soil solution and soil samples; Christine Herzlieb
maintained the compartment system experiment. We are grateful to the staff of the Klein-Altendorf Research station; and to the
coordination team (Timo Kautz, Miriam Athmann) of FOR 1320 at University of Bonn. The study was funded by Deutsche
Forschungsgemeinschaft (research group FOR 1320).

References

Andrist-Rangel Y, Simonsson M, Andersson S, Oborn I, Hillier S (2006) Mineralogical budgeting of potassium in soil: a basis for
understanding standard measures of reserve potassium. J Plant Nutr Soil Sci 169:605-615

Barre P, Velde B, Abbadie L (2007) Dynamic role of "illite-like" clay minerals in temperate soils: facts and hypotheses.
Biogeochemistry 82:77-88

Claassen N, Jungk A (1982) Kaliumdynamik im wurzelnahen Boden in Beziehung zur Kaliumaufnahme von Maispflanzen. J Plant
Nutr Soil Sci 145:513-525

Comerford NB (2005) Soil factors affecting nutrient bio-availability. In: BassiriRad H (ed) Nutrient Aquisition by plants. An Ecological
Perspective. Springer, Berlin, pp 1-14

Cox AE, Joern BC (1997) Release kinetics of non-exchangeable potassium in soils using sodium tetraphenylboron. Soil Sci
162:588-598

Cox AE, Joern BC, Roth CB (1996) Nonexchangeable ammonium and potassium determination in soils with a modified sodium
tetraphenylboron method. Soil Sci Soc Am J 60:114-120

Cox AE, Joern BC, Brouder SM, Gao D (1999) Plant-available potassium assessment with a modified sodium tetraphenylboron
method. Soil Sci Soc Am J 63:902-911

Evangelou VP, Lumbanraja J (2002) Ammonium-potassium-calcium exchange on vermiculite and hydroxy-aluminum vermiculite. Soil
Sci Soc Am J 66:445-455

Gaiser T, Perkons U, Kiipper PM, Uteau Puschmann D, Peth S, Kautz T, Pfeifer J, Ewert F, Kopke U (2012) Evidence of improved
water uptake from subsoil by spring wheat following lucerne in a temperate humid climate. Field Crops Res 126:56-62

Gottlein A, Hell U, Blasek R (1996) A system for microscale tensiometry and lysimetry. Geoderma 69:147-156

Hinsinger P, Jaillard B (1993) Root-induced release of interlayer potassium and vermiculitization of phlogopite as related to
potassium depletion in the rhizosphere of ryegrass. J Soil Sci 44:525-534

Hinsinger P, Barros ONF, Benedetti MF, Noack Y, Callot G (2001) Kaolinite formation from palygorskite and sepiolite in rhizosphere
soils. Geochim Cosmochim Acta 65:137-152

Hinsinger P, Bengough AG, Vetterlein D, Young IM (2009) Rhizosphere: biophysics, biogeochemistry and ecological relevance. Plant
Soil 321:117-152

Jaillard B, Ruiz L, Arvieu J-C (1996) pH mapping in transparent gel using color indicator videodensitometry. Plant Soil 183:85-95

Jobbagy EG, Jackson RB (2001) The distribution of soil nutrients with depth: global patterns and the imprint of plants.
Biogeochemistry 53:51-77

Kahle M, Kleber M, Jahn R (2002) Review of XRD-based quantitative analyses of clay minerals in soils: the suitability of mineral
intenstity factors. Geoderma 109:191-205

Lucas Y (2001) The role of plants in controlling rates and products of weathering: importance of biological Pumping. Ann Rev Earth
Planet Sci 29:135-163

Lumbanraja J, Evangelou VP (1990) Binary and tenary exchange behaviour of potassium and ammonium on Kentucky subsoils. Soil
Sci Soc Am J 54:698-705

Mikutta R, Kleber M, Kaiser K, Jahn R (2005) Removal of organic matter from soil using hydrogen peroxide, sodium hypochlorite and
disodium peroxidisulfate reexamined: a review. Soil Sci Soc Am J 69:120-135

Mitsios IK, Rowell DL (1987) Plant uptake of exchangeable and non-exchangeable potassium. II. Influence of soil type on uptake by
onion roots. J Soil Sci 38:65-70

Moore DM, Reynolds RC (1997) X-ray Diffraction and the Identification and Analysis of Clay minerals. Oxford University Press, New
York, 378 pp

Moritsuka N, Yanai J, Kosaki T (2004) Possible processes releasing nonexchangeable potassium from the rhizosphere of maize.
Plant Soil 258:261-268

Niederbudde E, Fischer WR (1980) Clay mineral transformations in soils as influenced by potassium release from biotite. Soil Sci
130:225-231

Norouzi S, Khademi H (2010) Ability of alfalfa (medicago sativa L.) to take up potassium from different micaceous minerals and
consequent vermiculitization. Plant Soil 328:83-93

Scherer HW, Ahrens G (1996) Depletion of non-exchangeable N[H.sub.4] in the soil-root interface in relation to clay mineral
composition and plant species. Eur J Agron 5:1-7

Schneider A (1997) Influence of soil solution Ca concentration on short-term K release and fixation of a loamy soil. Eur J Soil Sci
48:513-522

Scott AD, Hunziker RR, Hanway JJ (1960) Chemical extraction of potassium from soils and micaceous minerals with solutions
containing sodium tetraphenylboron. Soil Sci Soc Am Proc 24:191-194

Simonsson M, Andersson S, Andrist-Rangel Y, Hillier S, Mattsson L, Oborn I (2007) Potassium release and fixation as a function of
fertilizer application rate and soil parent material. Geoderma 140:188-198

Smith SJ, Scott AD (1966) Extractable potassium in grundite illite: I. Method of extraction. Soil Sci 102:115-122

Springob G, Richter J (1998a) Measuring interlayer potassium release rates from soil materials. I. Critical evaluation on the use of
resin and other batch procedures for determining kinetic data. J Plant Nutr Soil Sci 161:315-322

Springob G, Richter J (1998b) Measuring interlayer potassium release rates from soil materials. II. A percolation procedure to study
the influence of the variable 'solute K' in the <1... 10 [micro]M range. J Plant Nutr Soil Sci 161:323-329

Tice KR, Graham RC, Wood HB (1996) Transformations of 2:1 phyllosilicates in 41-year-old soils under oak and pine. Geoderma
70:49-62

Tributh H, Boguslawski E, Lieres A, Steffens D, Mengel K (1987) Effect of potassium removal by crops on transformation of illitic clay
minerals. Soil Sci 143:404-409

Velde B, Peck T (2002) Clay mineral changes in the morrow experimental plots, University of Illinois. Clays Clay Miner 50:364-370

Vetterlein D, Jahn R (2004a) Gradients in soil solution composition between bulk soil and rhizosphere--In situ measurement with
changing water content. Plant Soil 258:307-317

Vetterlein D, Jahn R (2004b) Combination of micro suction cups and time-domain reflectrometry to measure osmotic potential
gradients between bulk soil and rhizosphere at high resolution in time and space. Eur J Soil Sci 55:497-504

Vetterlein D, Marschner H, Horn R (1993) Microtensiometer technique for in situ measurements of soil matric potential and root water
extraction from a sandy soil. Plant Soil 149:263-273

Wang JG, Zhang FS, Zhang XL, Cao YP (2000) Release of potassium from K-bearing minerals: effect of plant roots under P
deficiency. Nutr Cycl Agroecosyst 56:45-52

Wentworth SA, Rossi N (1972) Release of potassium from layer silicates by plant growth and by NaTPB extraction. Soil Sci
113:410-416

Responsible Editor: N. Jim Barrow.

Electronic supplementary material The online version of this article (doi:10.1007/s11104-013-1680-6) contains supplementary
material, which is available to authorized users.

D. Vetterlein ([mail])

Department of Soil Physics, Helmholtz Centre for Environmental Research--UFZ, Theodor-Lieser-Str. 4, 06120 Halle/Saale, Germany

e-mail: doris.vetterlein@ufz.de

D. Vetterlein * T. Kiihn * K. Kaiser * R. Jahn

Soil Science, Martin-Luther-University Halle-Wittenberg, Von-Seckendorff-Platz 3, 06120 Halle/Saale, Germany

Table 1 Selected characteristics of Haplic Luvisols at Klein-Altendorf, Germany. Values represent means of three soil
profiles within the area of trial A (see Gaiser et al. 2012). Standard errors for the three profiles are given in
brackets. The analyses of Bt horizon material from 45-75 cm depth used in compartment experiment are given at the bottom
of the table Depth Horizon Bulk density pH [cm] [g [cm.sup.-3]] (Ca[Cl.sub.2]) 0-31 Ap 1.19 (0.07) 6.40 31-42 Al/Bt 1.25
(0.14) 6.68 42-63 Bt1 1.45 (0.07) 6.86 63-86 Bt2 1.43 (0.06) 6.93 86-116 Bwt 1.45 (0.04) 7.06 116+ leCw 1.47 (0.04) 7.32
Experiment Bt 7.23 Depth CaC[O.sub.3] Sand [g Silt [g [cm] [g [kg.sup.-1]] [kg.sup.-1]] [kg.sup.-1]] 0-31 < 1 (0.0) 70
(15) 755 (15) 31-42 < 1 (0.0) 59 (6) 744 (13) 42-63 < 1 (0.0) 37 (4) 674 (6) 63-86 < 1 (0.0) 34 (3) 647 (10) 86-116 < 1
(0.0) 42 (8) 683 (12) 116+ 130.0 (7.5) 50 (4) 753 (14) Experiment < 1 (0.0) 38 (3) 680 (4) Depth Clay [g CEC [C.sub.org]
[g [cm] [kg.sup.-1]] [[mmol.sub.c] [kg.sup.-1]] [kg.sup.-1]] 0-31 176 (10) 97.3 (11.1) 10.6 (0.8) 31-42 197 (17) 102.3
(14.8) 5.8 (0.4) 42-63 289 (7) 141.5 (19.6) 4.2 (0.1) 63-86 319 (8) 158.8 (12.6) 3.4 (0.0) 86-116 275 (19) 146.7 (15.6)
2.7 (0.1) 116+ 197 (18) 86.9 (14.0) 4.7 (0.4) Experiment 283 (2) 170.6 (9.1) 4.9 (0.1) Depth K exchangeable K "non- K
total [g [cm] [g [kg.sup.-1]] exchangeable" [kg.sup.-1]] [g [kg.sup.-1]] 0-31 0.20 (0.03) 3.20 (0.24) 17.68 (0.48) 31-42
0.11 (0.02) 3.49 (0.18) 18.41 (0.39) 42-63 0.09 (0.01) 3.99 (0.19) 19.87 (0.49) 63-86 0.09 (0.01) 4.32 (0.22) 19.80
(0.63) 86-116 0.07 (0.00) 4.18 (0.23) 18.68 (0.22) 116+ 0.05 (0.01) 3.61 (0.25) 15.40 (0.59) Experiment 0.07 (0.00) 3.98
(0.03) 20.15 (0.11)

----------

Please note: Illustration(s) are not available due to copyright restrictions.

Copyright: COPYRIGHT 2013 Springer

http://www-springer-com.ez13.periodicos.capes.gov.br/life+sciences/plant+sciences/journal/11104
Citação da fonte (MLA9)
Vetterlein, Doris, et al. "Illite transformation and potassium release upon changes in composition of the rhizophere soil solution." Plant
and Soil, vol. 371, no. 1-2, Oct. 2013, p. 267. Gale Academic OneFile,
link.gale.com/apps/doc/A354199688/AONE?u=capes&sid=bookmark-AONE&xid=efdc8ce3. Accessed 23 Aug. 2022.
Número do documento Gale: GALE|A354199688