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Abstract: The foliar absorption by field bean (Viciu fubu L.) of triclopyr-
triethylamine from solutions containing an organosiiicone surfactant, ' Silwet L-
77' at O, 1.0, 2.5 and 5.0ml litre-l, was investigated using fluorescence and
radiotracer studies. Physical characteristics such as formulation surface tension
and contact angles of droplet formed on the field bean leaf were determined and
combined to obtain a critical surface tension value (yCrltlpa,)of 19.5-22.9 mN m-'
for the adaxial leaf surface. The apparent surface tensions of the three formulations
containing L-77 were equivalent and low, an average of 22 mN m-l, which would
be sufficiently low to permit stomatal infiltration. The presence of L-77 at 2.5 or
5.0 ml litre-' significantly enhanced the uptake of triclopyr-triethylamine into
the leaf, particularly via stomatal pore regions. However, stomatal uptake from
solutions containing 0 or 1.0 ml litre-' L-77 was limited or non-existent. A
phenomenon termed 'adsorptive dilution ' is proposed to explain the absence of
stomatal infiltration with the 1.0 ml litre-' formulation. This involves a migration
of surfactant from the bulk solution to the expanding droplet surfaces as the
droplet spreads. This dilutes the surfactant concentration within the bulk solution,
which can in turn increase surface tension.
formation has been known to cause marked changes in 2.2 Fluorescence microscopy
surfactant characteristia6 However, this may be of less
importance with organosilicone surfactants such as Solutions of triclopyr-triethylamine with L-77 at 0, 1.0,
' Silwet ' L-77 since their micelle formation is very 2.5, and 5.0 ml litre-' plus 'Uvitex' 2B (Ciba-Geigy), a
different to that of the traditional surfactants.? fluorescent indicator, at 1 g litre-' were prepared. Leaves
L-77 is an organosilicone surfactant known for its were treated with 4 ~ 0 . pl 5 droplets, 5-10 mm away
dramatic effect in reducing surface tension of spray from the leaf midrib. At selected times (1 and 60 min),
solutionss, and its ability to enhance the performance of treated leaves were first rinsed with deionised water, then
herbicides in the control of certain weed species."-" The with methanol+water (70+30 by volume). The two
mode of action of L-77 has been linked to the promotion rinses were carried out to ensure that no herbicide
of herbicide uptake via stomatal pores.'O' "-15 residue remained on the leaf surface. Rinsed leaves were
Many researchers have observed the lack of correlation gently dried with clean tissue and mounted onto glass
between surface tension and wetting characteristics of slides for observation. Herbicide solutions were detected
herbicide formulations and their perf~rmance.~, 16, l 7 In using a Zeiss fluorescence microscope with a UV
this study the surface tension and wetting characteristics excitation source and representative photomicrographs
of a triclopyr-triethylamine formulation with various were obtained of herbicide absorption within the droplet
concentrations of the organosilicone surfactant, L-77, area.
were investigated and related to absorption by field bean Image analysis was then used to quantify the mean
(Vicia fuba L.) leaves. This species was selected as a areas of herbicide absorption in each photomicrograph
model plant species for gorse (Ulex europaeus L.), a as shown by the fluorescent indicator. The system was an
significant woody weed problem in New Zealand. Field image analysis package (PC-Semper, Synoptics Ltd.,
bean's uptake behaviour with a number of triclopyr- Cambridge, UK) with attached camera and video
organosilicone formulations was found to be similar to monitors, capable of scanning images of up to 512 x 512
that of gorse, and a number of similarities in stomatal pixels with 256 grey levels. Threshold intensities were
architecture between gorse and field bean were observed. selected to obtain a scanned video image as close to the
Field bean grows rapidly, and is very suitable for uptake, micrograph as possible. The mean values for degree of
translocation and many physicochemical studies.ls herbicide absorption were expressed for each treatment
The use of a Zisman plot enabled the critical surface as (1) area of absorption as a percentage of whole
tension value for the field bean leaf surface to be photomicrograph area, and (2) absorption area (mm2)in
determined and hence those triclopyr formulations likely whole photomicrograph area.
to infiltrate stomatal pores could be predicted. An Transformations were performed on the data to
innovative interpretation of the results for surfactant validate the analysis of variance assumption of equal
behaviour within droplets enabled some interesting variances. A square root transformation of the area
conclusions to be drawn with regard to herbicide (mm') and a logit transformation ( y = loglo(x/(100-x)))
performance, surface tension, and L-77 concentration. on the percentage area were the most
In particular, calculations reveal the importance of an suitable. As statistical inferences were made on the
'adsorptive dilution' effect, whereby the increase in transformed data, standard errors of the transformed
droplet surface accompanying spreading causes sur- means are given (Table 1).
factant migration from the bulk to the surface, thus
lowering the effective surfactant concentration within the 2.3 Foliar uptake studies
bulk film. This in turn can alter the surface tension and
hence affect stomatal penetration. ['4C]Triclopyr-triethylamine solutions were made by
adding [I4C]triclopyr to a solution of triclopyr-
triethylamine (360 g a.e. litre-') made up at a rate
2 MATERIALS AND METHODS equivalent to 4 kg a.e. ha-' in 200 litre ha-'. Relative
concentrations of labelled and unlabelled triclopyr
2.1 Plant material were such that 1 pl of herbicide solution contained
20000-30000 dpm.
The field bean (Vicia faba L. cv. Maris Bead) seeds were Four formulations of amine were prepared with
pregerminated at 25°C on moist blotting paper for three surfactant concentrations of 0, 1.0, 2.5, and 5.0 g litre-'.
to four days prior to sowing. Plants were grown in 120- The single microlitre of formulation for each plant was
mm pots containing potting mix for two weeks in a applied as 4 x 0 . 2 5 ~ droplets,
1 2 h after the beginning of
controlled environment cabinet (day/night temperatures the light photoperiod. Eight replicate plants per treatment
21/15"C; 14: 10 h1ight:dark; 70-75% relative humidity; were used. After 1 or 6 h, bean leaves were washed with
light intensity 300 pmoles m-2 s-l). All formulation +
methanol + water (70 30 by volume) to determine the
applications to field bean plants were made to adaxial leaf percentage gross uptake. Immediately after the methanol
surfaces of the third leaf once it had fully expanded. wash, a second leaf wash with 10 ml of chloroform was
Surface tension in absorption of herbicide via leaf stomata 229
TABLE 2
Percentage Uptake (Gross, Wax and Net) of [14C]triclopyr-triethylamine
after 1 h and 6 h when Concentration of L-77 in the
Solution was Increased"
0.8 (4.9) 0.2 (2.6) 0.6 (4.2) 11.5 (19.6) 4.9 ( 12.4) 5.0 ( 12.6)
2.8 (9.5) 0.3 (3.0) 2.6 (9.0) 12.4 (20.4) 2.5 (8.7) 10.2 (18.5)
6.8 (14.7) 0.3 (3.3) 6.5 (14.3) 17.1 (24.4) 1.6 (7.0) 15.9 (23.5)
9.7 (18.1) 0.3 (3.2) 8.8 (17.2) 16.4 (23.8) 1.4 (6.7) 15.0 (22.8)
l.OO(l.11) 0.03 (0.14) 0.99 (1.15) 1.31 (1.12) 0.54 (0.92) 1.10 (1.02)
Arcsine transformed means are given in parentheses and standard errors (SE,) below.
230 R . D . Buick, G . D . Buchan, R . J . Field
determined by extrapolating a line of best fit for the significantly different from each other. The interaction
plotted data, back to where cosine 6, = 1 (see Fig. 3). between time and solution treatments was not significant.
A range of herbicide absorption levels was often
detected for a single treatment. This was reflected in the
3 RESULTS
large standard errors for some treatments in Table 1.
3. I Fluorescence microscopy 3.2 Foliar uptake studies
After both 1 and 60min washes, the control herbicide Gross and net uptake of ['4C]triclopyr-triethylamine was
solutions (i.e. no added L-77) had not penetrated the significantly increased above control after 1 h by the
adaxial surface of field bean leaves, shown by a relative inclusion of L-77 at any of the three concentrations
absence of blue fluorescent dye across their surfaces. The (Table 2). Incorporation into wax increased as the rate of
glandular hairs or trichomes and any dust particles on L-77 increased and was only significantly greater than
the leaves were the only parts which appeared to absorb control when the two higher concentrations were used
the fluorescent indicator and presumably the herbicide. (i.e. 2.5 or 5.0 ml litre-') (Table 2).
When L-77 was added to the triclopyr-triethylamine After 6 h, gross and net uptake of triclopyr-
solution at 1.0 ml litre-' there were some small and triethylamine was also increased by the addition of L-77
infrequent regions of herbicide absorption, mainly at all three concentrations. However, this increase was
associated with trichomes (after 1 and 60 min), but in only significantly above control with the 2 5 ml litre-'
some cases with stornatal pores after 60 min. By contrast, concentration for gross uptake and with any of the three
L-77 at 2.5 or 5.0 ml litre-' both induced similar extensive concentrations for net uptake. Of these three L-77
regions of herbicide uptake mainly associated with treatments, the 2.5 and 5.0 ml litre-' concentrations
stornatal pores, both after 1 and 60 min. Herbicide significantly improved net uptake above the value
damage to the leaf epidermal cells after 60 min with the with 1.0 ml litre-' surfactant. Incorporation into wax
two highest L-77 concentrations was characterised by decreased as the rate of L-77 increased, such that at the
large and brightly lit regions of indicator completely two highest surfactant concentrations, incorporation
covering the site of droplet application. into the wax was significantly less than that found in the
Image analysis found the mean area of triclopyr control. These results are discussed below in terms of
absorption was greater after 60 than after 1 min with all selecting an optimum concentration of L-77 to maximise
treatments (Table 1). Average absorptions as a per- the foliar uptake of triclopyr-triethylamine.
centage of total photograph area for 1 and 60min
treatments were 6.0 and 18.9% respectively. The dif- 3.3 Surface tension
ference between the times was most notable for 2.5 and
5.0 ml litre-' L-77 treatments (Table 1). The addition of a fluorescent indicator, 'Uvitex' 2B, did
Herbicide absorption areas were significantly greater not significantly alter the surface tension of any of
when 2 5 or 5.0 ml litre-' L-77 was added to the triclopyr- the triclopyr-triethylamine + L-77 solutions (data not
triethylamine solution. These two treatments were not shown). The surface tension of the triclopyr-
significantly different from each other (Table 1). Similarly triethylamine solution with no added surfactant was 63.4
the control and 1.0 ml litre-' L-77 treatments were not (k1.4) mN m-' but this was significantly reduced by the
addition of 'Silwet' L-77 (Fig. 1). At concentrations
greater than 0.5 ml litre-' there were no significant
.,i
-E 50
changes in surface tension from a mean of 22.8 mN m-'.
Thus, the largest decrease in surface tension occurred
with the addition of L-77 up to 0.5 ml litre-'. Surface
tension values were also plotted against logarithm of
surfactant concentration for L-77 in aqueous solution
and in the triclopyr-triethylamine solution (Fig. 2). A
double line or 'broken-stick' trend was obtained in both
cases. The right-hand observations were regressed, while
the left-hand mean observations (0.05 and 0 1 ml litre-')
were simply joined. In the case of L-77 in water solutions,
the regression equation was :
y = 22.6 - 3 . 0 9 ~ (R2= 62 Yo)
2ok ' 1' ' 2* ' 3' ' 4*
' 5
I
The triclopyr-triethylamine and L-77 formulations
'Silwet' L77 concentration (ml litre.') formed a regression line described by :
Fig. 1. Surface tension of triclopyr-triethylamine solutions
containing 'Silwet' L-77. Standard error of the mean = 0.71. y = 22.5-0482~ (R2= 31 O h )
Surface tension in absorption of herbicide via leaf stomata 23 1
451
contact angle (8,).
From this, the critical surface tension value (ycritica,)
r for the adaxial leaf surface of field bean was calculated as
21-1 mN m-l. Parallel curves fitted to provide 95%
confidence limits yielded a ycritical range of
19.5-22.9 mN m-' (Fig. 3). The implications and suit-
ability of the quadratic model are discussed below.
10' 100 10' results by the unexpectedly low uptake of herbicide from
'SiIwet' ~ 7 concentration
7 (ml litre-') solutions containing 1.0 ml litre-' L-77, despite the fact
Fig. 2. Surface tension of solutions of 'Silwet' L-77 in (A) that the corresponding surface tension should have been
water and in ( 0 )triclopyr-triethylamine solutions (log scale). below the critical value for stomata1 entry.
Bars = least significant differences. Linear regression to the Surfactant molecules tend to aggregate at the interface
surface tension results for 0.5, 1.0, 2.5 and 5 0 m l litre-' of different phase^.^.'^^^ Depending on the propensity of
L-77 solutions in water was: y = 2 2 6 3 . 0 9 ~(R2= 62%);
in triclopyr-triethylamine solution was : y = 22.5-0.482~ surfactant molecules to arrange themselves at these
(R2= 31 %). interfaces (which here include the solution-air and
solution-leaf interfaces), any increase in interface area
will produce a reduction in surfactant Concentration
within the bulk solution. The greater the spread of the
droplet, the greater will be the reduction in bulk
concentration. Here, the known details of the surface
adsorption of L-77 from solution were used in first-order
calculations (1) to establish that the film produced from
droplet spread was sufficiently thick to be considered
'macroscopic' within its bulk, and (2) to determine the
effective change in surfactant concentration within the
bulk solution (specifically for a droplet of 1.0 ml litre-'
L-77 close to the critical micelle concentration).
critical micelle concentration for L-77 in water.' If the below the break point of Fig. 2 created difficulties in
macroscopic assumption holds at this low concentration, accurately determining this Limiting slope in the present
then it would apply even more so at higher concentra- study, and the value of 70 A2 per molecule determined
tions, such as 0.5 or 1.0 ml litre-', for which the droplet elsewhere for an organosilicone similar to L-77 was
spreads were found to be e q ~ a 1 . l ~ used.'
Consider a total volume, K, of a solution of con- As the droplet spread, an adsorbed monolayer would
centration, C. The volume of surfactant, E,in the volume have been formed at the solid (leaf)-liquid interface. For
of water, V,, determines the concentration. a polyethylene-water interface, the area is approximately
50 A* per m o l e ~ u l eIn
. ~ the absence of a measured value
i.e. I/I= K+V, for adsorption at the leaf-liquid interface, the value for
and c =y / y polyethylene, which, as a hydrocarbon polymer, should
have similar physical properties to cuticular wax, was
The mass of L-77 is rn, = p , . K where p, =
used. A wax is an ester formed from a long-chain alcohol
1.007 x lo3 kg mP3.'
and a long-chain acid, and thus has hydrocarbon
The molecular weight (M,) of L-77 is = 0.620, so
structure along most of its length. The surface adsorp-
the number, N , of L-77 molecules in the total volume (VJ
tions (kg m-*) of L-77 at the liquid-vapour interface (slJ
is given by:
and at the solid-liquid interface (s,J were then deter-
N = (m,/M,). N , mined using:
where N, = Avogadro's number = 6.022 x loz3mol-'. Surface adsorption (s) =
These N molecules will be spread throughout the volume Mass of one L-77 molecule
I/I. Thus, each molecule can be taken to occupy on Area per molecule at the interface
average a cubical 'cell' of side I and volume P where: The surface adsorption at the liquid-vapour interface is:
1= (y/N)'j3
1.0296x
s, =
=( . MJp,. K. N,)"' 70 x 10-2"
= (M,/p, N , . C)"3 = 1.47 x kg m-z
= (0.620/1.007 x lo3 x 6,022 x loz3x 2 x The corresponding surface adsorption of L-77 at the leaf
= 1.72 x rn surface is
Thus, approximately 400 (i.e. 6.8 x 10-6/1.72 x 1.0296 x
SS1 =
molecules of L-77 could be aligned within the thickness 50 x lo-'''
of the droplet film. Therefore, the film could be = 2-06 x kg m-'
considered to be of macroscopic thickness.
The final step is to estimate the reduction in the
3.5.2 Change in bulk concentration due to spreading concentration of L-77 within the droplet. As the droplet
In order to investigate the unexpectedly low uptake of spreads, adsorption into both the interfaces would
triclopyr-triethylamine at the 1.0 ml litre-' L-77 con- produce an 'adsorptive dilution' effect in the bulk
centration, the effective change in concentration of the solution. The bulk concentration, C (in this case
bulk solution within the droplet was calculated for that 1.0 ml litre-') would reduce to C' estimated using the
concentration, using results of the fluorescence and following equation :
radiotracer studies. The following data were employed in
the calculation:
1. The volume of formulation applied to the leaf,
V = 0 . 2 5 ~ 1 (for each of the four replicate x (1.47 + 2.06) x
= 10-3- 37 x
droplets applied). 1.007 x lo3 x 2 3 x 10-lo
2. The mean droplet spread or area ( A ) of 0 . 2 5 ~ 1
drops was found to be 37.0 mm2 = 37 x m*.15 = 10-3(1 - o m )
3. The density of L-77, p, = 1.007 x lo3 kg m-3.9 = 0.000481
4. The area per molecule in tbe monolayer at the
liquid-vapour interface is 70 Az = 70 x lo-'' m2per = 0.48 ml litre-'
molecule).'
Thus, in this case, the bulk concentration is more than
The latter area can be deduced from the limiting slope of halved. Note that the value of A used is the apparent
the log concentration-surface tension plot (see Fig. 2) foliar spread of the droplet. The actual contact area
and the Gibb's equation. However, a deficiency in points could be considerably larger, due to leaf surface
Surface tension in absorption of herbicide via leaf stomata 233
microtopography, which would accentuate the above In the case of organosilicone surfactants, micelle
adsorptive dilution. formation has been found to be limited, with the number
of surfactant molecules in a micelle being as few as 5 to
lo.',' This contrasts with conventional organic surfact-
ants which typically have aggregation numbers ranging
4 DISCUSSION from 20 to 140.7In fact, an organosilicone surfactant,
like L-77, may not form regular micelles at all.26As a
Volatilisation losses of triclopyr have been found to be consequence, micellisation may be of minimal import-
1ow,22,23 with amine formulations generally exhibiting ance for L-77 mixtures in terms of biological activity of
smaller losses than ester formulation^.^^ As a result, the the overall formulation.
risk of triclopyr losses from field bean leaves was not Surface tension and contact angle results were used to
considered significant in these uptake studies. find a critical surface tension value (ycritical) for the field
Fluorescence (Table 1) and radiotracer (Table 2) bean leaf and formulations used. Contact angles and
studies revealed that greatest absorption of triclopyr surface tension have become frequently used measure-
occurred when L-77 was included in the solution at 2.5 ments to predict surface wetting and spreading on plant
and 5.0 ml litre-'. The strong association of absorbed surfaces.17.2 0 , 2 7 , 2 8 ycriticalis the surface tension at which
material with stomatal pore regions at these two the cosine of the contact angle (0,)is unity, i.e.
concentrations further supported the mode of action of 0,= Oo.20 For the adaxial leaf surface of field bean
L-77 involving the promotion of stomatal infiltra- with triclopyr-triethylamine and L-77 solutions, the
t i ~ n . ' ' * ' ~ ' 'In
~ contrast, the control solution (no sur- critical value range was 19.5-22.9 mN m-l (mean of
factant) was absorbed only by glandular trichomes, 21.1 mNm-') (Fig. 3). Schonherr and Bukovac' found
surface dust or lesions. The 1.0 ml litre-l L-77 treatment ycritical = 25-30 mN m-' for the lower leaf surfaces of 2.
also appeared to enter trichomes and lesions, but purpusii while Stevens and BukovacZ9found 29 mN m-'
absorption via stomatal pore regions was limited and for adaxial maize leaves. The variation in ycritical values
only apparent after 1 h, despite the fact that the surface could be due to a number of reasons. Firstly, different
tension corresponding to this bulk concentration was plant species will differ in chemical composition and
essentially the same as for concentrations of 2.5 and spatial arrangement of wax c o n ~ t i t u e n t s . ~Stevens ~~~~~~'
5.0ml litre-' (Fig. 1). The relatively low uptake of and BukovacZ9discuss how the value of 29mNm-'
['4C]triclopyr-triethylamine at the 1.0 ml litre-' L-77 seemed high for a very hydrophobic surface like maize
concentration (Table 2) also suggested that a limited leaves, but they suggested that water repellency of these
amount of active ingredient was able to enter the leaf, leaves is enhanced by epicuticular wax platelet^.'^ Abbott
particularly after 1 h. Although the 2.5 and 5-0 ml litre-' et aL3' discuss how surface wax roughness greatly
concentrations of L-77 seemed to be optimum for influences ycritiCal values. Furthermore, the kinds of
triclopyr-triethylamine absorption, evidence exists that surfactant solution being studied are important deter-
L-77 at 5.0ml litre-' may have a negative effect on minants of the critical surface tension value. The above
translocation processes.", 18,25"3 r e s e a r c h e r ~ studied
~ ~ ~ ~ different solutions which were
A significant reduction in the surface tension of the different again to the triclopyr solutions used here. A
triclopyr-triethylamine solution was observed when very lower yCritiCal value would be expected if the triclopyr
low concentrations of the organosilicone surfactant, formulations dissolved the surface waxes of field bean31
L-77, were added (Fig. 1). A plateau minimum surface which was observed with scanning electron micrographs
tension was reached at approximately 22 mN m-l. A where the bean leaf surface appeared to be disrupted or
dramatic reduction in surface tension is typically obser- broken down by triclopyr form~lations.'~ Another aspect
ved when surfactants are added to solution^^-^ but the to consider in determining yCriticalvalues is the hydrogen-
magnitude of reduction tends to be greatest for organo- bonding properties of liquids, since this has been found
silicone surfactants.'. l8
3' important in the prediction of spreading3'
Some surfactants induce quite significant changes in Zisman plots typically form a rectilinear relation
behaviour when concentrations reach or exceed the between the cosine of the contact angle and the surface
CMC6 The formation of micelles in a solution causes a tension for a solution series.20s28Determination of the
sharp change in many physical proper tie^,^ of which critical surface tension of liquids from such plots has
surface tension is just one, and may affect the biological proved useful in describing the spreading behaviour of
activity of the formulation.6 Figure 2 displays a sudden various liquids on a surface. Critical values have also
break-point or inflexion in surface tension as surfactant been related to the constitution of various low-energy
concentration is increased, occurring approximately at surfaces. As found with field bean, a critical surface
2.0 ml litre-' L-77 for both the amine and water solutions. tension (yCritiCal)of 19.5-22.9 mN m-' on a hydrocarbon
Goddard and Padmanabhang estimated the CMC for a surface is a low value. Shafrin and Zisman" suggest that
similar organosilicone surfactant in water to be around these values are typically found with surfaces composed
this concentration. of closely packed methyl groups.
234 R . D.Buick, G.D.Buchan, R. J. Field
Although this rectilinear relationship is true for most normal bulk aqueous solution, and the surface tension
solutions on most surfaces, the band of data may exhibit data for macroscopic droplets (Figs 1 and 2) can be used
concave curvature for values above 50 mN m-' on some in investigations of film behaviour.
low-energy surfaces.2oThis was observed with adaxial A deficiency in points below the break point of Fig. 2
leaf surfaces of field bean and was consistent with the created difficulties in accurately determining the limiting
observation that the quadratic curve best described the slope and hence the area per moleculeoof L-77, using
relationship (Fig. 3). Up to 45-50 mN m-l the points on Gibb's equation. Thus, the value of 70 A' per molecule,
the Zisman plot formed a linear band, but above this determined by Goddard and Ananthapadmanabhan' for
surface tension, the relationship tended to curve up- an organosilicone similar to L-77, was used to calculate
wards. It has been shown that such curvature results a surface adsorption of 1-47x kg m-' for L-77 at the
from weak hydrogen bonds forming between the molec- solution-air interface.
ules of liquid and those in the solid s ~ r f a c e . However,
~' Similarly, as the droplet spread, an adsorbed mono-
it should be noted that in this case the quadratic curve layer was formed at the solid (leaf)-liquid interface.
fitted to the cosine @,-surface tension plot was strongly Measurements by Goddard and Padmanabhan' in-
influenced by only one data point above 40 mN m-'. dicated that for a polyethylene-water interface tke
Three of the points were below 40 mN m-', improving adsorption monolayer packed to approximately 50 A'
the precision of the critical surface tension value per molecule. Assuming that this value was appropriate
calculated from this part of the curve. for adsorption at the leaf-solution interface, the cor-
Schonherr and Bukovac' established that stornatal responding adsorption of L-77 at the plant surface was
entry of liquids depends on three main factors: the found to be 2.06 x kg m-'.
surface tension of the liquid, the contact angles of the As the droplet spread, adsorption into both the
liquid on the plant surface, and the stornatal pore wall liquid-vapour and surface-liquid interfaces produced an
morphology. According to their model for stomatal 'adsorptive dilution' effect in the bulk solution. The
entry, the surface tension must be lower than the critical above estimates suggest that a droplet of 1.0 ml litre-'
surface tension value for that plant and liquid. L-77 solution would actually have had an effective bulk
Triclopyr-triethylamine solutions containing 1.0, 2.5 or concentration after spreading of about 0.48 ml litre-', or
5.0 ml litre-' L-77 all appeared to have surface tension even less if the actual droplet contact area exceeded the
values at or below the critical value for field bean and this apparent area used in the calculation. This is in the most
aqueous system, so would be expected to enter stornatal sensitive region of the surface tension-concentration
pores. Transmission electron microscopy found field curve (Fig. 1) with an apparent surface tension value
bean's stornatal pore walls had angles which would similar to the 0.5 ml litre-' solution. The resulting
provide positive pressure differences with the three decrease in bulk concentration may have been sufficient
triclopyr-triethylamine/L-77 solutions, thus permitting to raise surface tension to a value above the critical value
instantaneous stornatal infiltration.l8 However, the (ycritica,), thus inhibiting stornatal entry and herbicide
fluorescence results did not display appreciable levels absorption via this pathway. For 2.5 and 5.0 ml litre-'
of stornatal entry with the solution containing solutions, a reduction in effective concentration within
1.0 ml litre-' L-77. The two higher concentrations (2.5 the drop could cause a shift to the left along the
and 5.0 ml litre-') certainly did facilitate stornatal entry, concentration axis (Fig. 1) but as the onset of the plateau
so cursory reasoning suggests that surface tension is occurred well before the 2.5 ml litre-' value, effective
unable to fully explain the mechanism by which L-77 surface tension would have been substantially unaltered,
enhanced herbicide performance. A lack of correlation remaining well below yCritiCaI. This would allow stornatal
between measured surface tension and performance infiltration with the two higher concentrations of
of formulations has been observed by several surfactant, according to Schonherr and Bukovac's
researchers.6*'6il7 model.' In practical terms, herbicide solutions may need
The above investigation into surfactant behaviour in to have a sufficiently high concentration of L-77 (i.e. well
solution has helped to explain this observation. Sur- above the inflexion point in the surface tension-log
factant molecules tend to aggregate at ~urfaces,~~'' thus concentration plot). If the concentration is, for material
tending to reduce their effective concentration within the economy, selected too close to this point, stomatal
bulk solution. Estimates of this change in bulk con- infiltration may be rendered ineffective.
centration, and therefore surface tension, following Estimating the adsorptive dilution effect has helped to
droplet spreading were determined by considering details explain why the 1.0 ml litre-' L-77 solution was unable to
of the surface adsorption. induce absorption in the same way as the 2.5 and
Initially it was established that the film after spreading 5.0 ml litre-' solutions. However, these calculations
had 'macroscopic' thickness, t , since t was found to be assume that micelle formation did not significantly
much greater than the average distance between sur- alter the behaviour of surfactant solutions. Although
factant molecules in solution. The film of aqueous organosilicone surfactants tend not to form regular and
solution between surfactant monolayers behaves as large micelle~,'~'~ it is not known whether the occurrence
Surface tension in absorption of herbicide via leaf stomata 235
of even limited micellisation with L-77 in triclopyr- tions of Aqueous Surfactant Systems. National Bureau of
triethylamine would actually affect surfactant-enhanced Standards, Washington DC, 1971, pp. 1-21.
6. Parr, J. F. & Norman, A. G., Bot. Gaz., 56 (1965) 26.
uptake of the herbicide via stomata. Micellisation may 7. Schwarz, E. G. & Reid, W. G., Ind. Engng Chem., 56
affect the calculations made above, although the small (1964) 26.
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