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

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6.3 Diffusion with Changing Donor Concentrations: The Transient State 185<br />

Diffusion coefficient (m 2 /s)<br />

2.5e-18<br />

2.0e-18<br />

1.5e-18<br />

1.0e-18<br />

5.0e-19<br />

0.0<br />

Thickness <strong>of</strong> sorption compartment (µm)<br />

2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0<br />

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0<br />

Thickness <strong>of</strong> limiting skin (µm)<br />

Fig. 6.19 Effects <strong>of</strong> thicknesses <strong>of</strong> cuticular compartments on diffusion coefficient. Total thickness<br />

<strong>of</strong> cuticle is 3µm, <strong>and</strong> rate constant was taken to be 1 × 10 −6 s −1<br />

dissolved initially. It is implicitly assumed that desorption from the outer surface is<br />

not limited by diffusion in anticlinal pegs <strong>and</strong> other portions <strong>of</strong> the sorption compartment<br />

remote from the limiting skin. This can be taken for granted as long as<br />

diffusion coefficients in the limiting skin is 50–100 times lower than in the sorption<br />

compartment. Whenever this is the case, desorption plots (Fig. 6.18) are linear, <strong>and</strong><br />

in this case there is no need to worry.<br />

Using simultaneous bilateral desorption, the diffusion coefficient <strong>of</strong> 2,4-D in the<br />

sorption compartment was estimated to be 10 −14 to 10 −15 m 2 s −1 (Fig. 6.15). D values<br />

estimated from Fig. 6.18 are 10 −18 to 10 −19 m 2 s −1 , which is lower by more<br />

than three orders <strong>of</strong> magnitude. We can also estimate D in the sorption compartment<br />

using unilateral desorption. If PCP is desorbed from the inner surface <strong>of</strong> the<br />

CM a nonlinear plot is obtained with an initial slope <strong>of</strong> 0.0017s −1 (Fig. 6.20). This<br />

is larger by a factor <strong>of</strong> 944 than measured for desorption from the outer surface<br />

(Fig. 6.18). Rate constants decrease with time, because the sorption compartment is<br />

heterogeneous, as was seen already in Fig. 6.15. Desorption from the outer surface<br />

<strong>of</strong> MX-membrane was also non-linear, <strong>and</strong> linearity lasted only for 2 h (Fig. 6.20).<br />

The initial rate constant was 155 times larger than that measured with Citrus CM.<br />

After 2 h, rate constants decreased because diffusion in the sorption compartment<br />

became rate-limiting. Comparing the initial slope obtained with MX with that <strong>of</strong><br />

UDIS demonstrates that PCP mobility in the outer layer <strong>of</strong> extracted CM is lower<br />

by a factor <strong>of</strong> 6 than mobility in the sorption compartment (UDIS). This difference<br />

is too small to guarantee linear desorption plots until membranes are empty.<br />

Apparently, diffusion from the anticlinal pegs to the outer layer <strong>of</strong> the MX was too

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