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Water and Solute Permeability of Plant Cuticles: Measurement and ...

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164 6 Diffusion <strong>of</strong> Non-Electrolytes<br />

Table 6.5 Distribution <strong>of</strong> PCP in the compartments (CPT) <strong>of</strong> barley leaves as affected by duration<br />

<strong>of</strong> preloading. CPT1 <strong>and</strong> CPT2 were obtained by non-linear regression analysis (6.10). CPT3 is the<br />

fraction <strong>of</strong> PCP unaccounted for by CPT2 <strong>and</strong> CPT1<br />

Preloading for CPT1 CPT2 CPT3<br />

30 min 0.56 0.10 0.34<br />

90 min 0.41 0.08 0.51<br />

180 min 0.15 0.10 0.75<br />

Desorption kinetics were analysed by non-linear regression. The best fit (r 2 ><br />

0.99) was obtained with a model consisting <strong>of</strong> two compartments (CPT1 <strong>and</strong> CPT2)<br />

<strong>and</strong> two rate constants (k1 <strong>and</strong> k2):<br />

Mt<br />

M0<br />

= CPT1<br />

� � � �<br />

−k1t −k2t<br />

1 − e +CPT2 1 − e . (6.10)<br />

Rate constants were independent <strong>of</strong> duration <strong>of</strong> preloading, <strong>and</strong> amounted to 8.5 ×<br />

10 −3 <strong>and</strong> 3.7 ×10 −4 s −1 for k1 <strong>and</strong> k2 respectively. Rate constants were defined by<br />

(2.6). From the rate constant, the half-time (t 1/2) required for 50% sorption or desorption<br />

(Mt/M0 = 0.5) can be calculated as t 1/2 = ln 0.5/k. Hence, t 1/2 is 81.5 <strong>and</strong><br />

1,873 s for compartments 1 <strong>and</strong> 2 respectively. It takes about five half-times before<br />

the compartments are empty. In the case <strong>of</strong> barley leaves <strong>and</strong> PCP this amounted to<br />

6.8 <strong>and</strong> 156 min for compartments 1 <strong>and</strong> 2, respectively.<br />

The compartment sizes in (6.10) represent fractions. The absolute size <strong>of</strong> a<br />

compartment in Bq is obtained by dividing radioactivity in the CPT by total radioactivity<br />

in the leaf. The fractions <strong>of</strong> PCP contained in the compartments are given in<br />

Table 6.5.<br />

Sizes <strong>of</strong> CPT1 <strong>and</strong> CPT3 depended on duration <strong>of</strong> preloading, while CPT2 was<br />

constant <strong>and</strong> 8–10% <strong>of</strong> total PCP was sorbed in this compartment. CPT1 decreased<br />

<strong>and</strong> CPT3 increased with duration <strong>of</strong> preloading. PCP in CPT1 <strong>and</strong> CPT2 was<br />

reversibly sorbed, while PCP in CPT3 increased with time <strong>and</strong> could not be recovered<br />

from the leaves. This indicates that this fraction <strong>of</strong> PCP was in the leaf tissue in<br />

dissociated form <strong>and</strong> was held there by an ion trap mechanism. pH in the apoplast<br />

<strong>and</strong> symplast are around 5–6, <strong>and</strong> this favours dissociation.<br />

If the absolute amounts contained irreversibly in CPT3 are plotted vs time, a<br />

straight line is obtained (Fig. 6.5, plot “calculated from desorption”) which intersects<br />

the origin <strong>and</strong> has the same slope as the plot “amount penetrated” vs time.<br />

Permeance calculated from desorption experiments is 1.4 × 10 −7 m s −1 , <strong>and</strong> is<br />

identical within experimental error to permeance obtained from the slope <strong>of</strong> a<br />

penetration experiment.<br />

The parallel displacement is caused by PCP reversibly sorbed on the leaf surface,<br />

in epicuticular wax <strong>and</strong> in the cuticle underneath (cutin <strong>and</strong> intracuticular wax).<br />

The donor solution is in contact only with the tips <strong>of</strong> the epicuticular wax crystallites.<br />

Hence, epicuticular waxes are filled first <strong>and</strong> serve as intermediate phase<br />

between aqueous donor <strong>and</strong> cuticle. PCP sorbed in wax continues to diffuse into the

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