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OF HERBICIDES
J. R. BAUR and R. W. BOVEY
Agricultural Research Service
U.S. Department o f Agriculture
and Department o f Range Science
Texas A &M University
College Station, Texas 77843
Recent interest in environmental protection, together with the need to increase the
efficiency of agricultural production, has led to the development of pesticide formula-
tions that are programmed for a controlled release of the toxicant. One such technique
hlvolves the inclusion of pinolene (13-pinene polymer) in the spray mixture, which is sub-
sequently polymerized by sunlight to produce a thin film that occludes the toxicant
molecule within its structure, thus protecting it from natural degradation factors
(Blazquez et al. 1970).
(60°C) or long-wave (356-nm) ultraviolet (uv) irradiation (Baur et al. 1973). During the
course of the previous studies (Baur et al. 1973), it became apparent that volatility losses
could constitute a large part of what appeared to be thermal degradation, especially of
dicamba. Herbicide losses by volatilization have been documented for several non-
ester herbicides, including ~,~,a-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine (trifluralin)
(Ketchersid et aL 1969); 2,6-dichlorobenzonitrile (dichlobenil) (Parochetti et al. 1971);
3-(3,4-dichlorophenyl)-l-methoxy-l-methylurea (linuron); and 2-chloro-4-(ethylamino)-
6-(isopropyl-amino)-s-triazine (atrazine) (Walker 1972).
The objectives of this research were (a) to examine the effects of heat and long-wave
uv irradiation on the urea-type compositions of (2,4-dichtorophenoxy)acetic acid (2,4-D)
and dicamba; and (b) to separate thermal degradation losses from volatility losses for the
urea-type compositions and conventional acid formulations of dicamba.
The urea-type compositions developed by Beasley and RhodO have polymeric charac-
teristics, although it is not possible at this time to assert unequivocally that they are true
polymers. Melting-point data, along with molecular-weight determinations, strongly indi-
cate polymeric structures. The molecular-weight data suggest that the urea-type composi-
tions consist of urea-herbicide units linked into chains whose molecular weight ap-
proaches 5,0002. Throughout this report we refer to the urea-type composition as
"polymer" with the knowledge that it may be a true polymer or simply a unique combi-
nation of components that result in altered herbicidal and degradative characteristics.
Reference to conventional formulation refers to solutions of "non-polymerized" 2,4-D or
dicamba.
Materials and m e t h o d s
Solutions. Analytical grade (100% purity) 2,4-D and technical grade (89.3% purity)
dicamba were used in all experiments. Except where specifically noted, all experiments
were carried out with acetone solutions of the respective herbicides.
Thermal exposure. One ml of solution containing either 11.0, 110.5, or 1,105 /ag of
either conventional or "polymeric" 2,4-D was pipetted into 50-mt beakers and allowed to
evaporate. The beakers were placed at random in an incubator set at 60 + I°C. Six repli-
cate beakers of each treatment were removed at 0-, 1/2-, 1-, 2-, 4-, and 7-day intervals.
Three experiments were carried out.
Nitrogen flow rates, measured twice daily, ranged from 53 to 66 ml/min for the ten
positions.
All experiments were carried out over a seven-day period. Four experiments were con-
ducted with ten replicate tubes containing conventional dicamba. A second series of three
experiments were carried out with five replicate tubes each of "polymeric" and conven-
tional dicamba.
Extraction and analysis. Herbicide residues from samples applied in acetone were re-
moved from the beakers (thermal-loss studies) and petri dishes (uv-degradation studies)
by washing with 50 ml of acetone. The wash effluent was collected in a 50-ml volumetric
flask and adjusted to volume.
'6
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co 0 ~ ,~
o_~=
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z > ~ o~i- o
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t~
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Ultraviolet and Volatility Loss of Herbicides 281
treatments were pipetted into 2.0-ml serum vials and reduced to dryness. Silylating
reagent was added directly to the serum vials at the time of GLC analysis (Baur et al.
1971).
Dicamba remaining in the U-tubes after a seven-day exposure to the volatilization con-
ditions was recovered by washing the tubes, serum caps, and respective glass connecting
tubes with acetone. The 60°C closed (nontubulated, Figure 1, point 5), and 60°C flow
(tubulated, Figure 1, point 6) tubes were washed with 50 ml of acetone. The paired cold-
trap tubes and the glass input and exit tubes (Figure 1, points 10, 11, 7, 14, respectively)
were washed with 100 ml of acetone. Acetone washes were brought to their respective
volumes in volumetric flasks. Aliquots of 0.5, 1.0, and 0.25 ml were taken from the cold-
trap, 60°C flow, and 60°C closed-tube washes, respectively, and evaporated in two-ml
serum vials. The trimethytsilyl ester of dicamba was prepared by adding the silylating re-
agent at the time of GLC analysis.
Seven-day exposure of the same levels of conventional 2,4-D reveals an inverse rela-
tionship between initial concentration and uv loss (Figure 3, D, E, F). The patterns for
"polymeric" 2,4-D indicate extreme sensitivity to uv light, with the majority of the loss
occurring during the first 12 hr (Figure 3, D, E, F), with little or no concentration de-
pendence. The pattern of loss for conventional 2,4-D is quite similar to that noted for
2,4,5-T in our earlier work (Baur et al. t973).
282 J . R . Baur and R. W. Bovey
It could be argued that the rapid loss of "polymeric" 2,4-D noted in Figure 3, D, E, F,
and Figure 4 was the result of either a chemical reaction peculiar to the "polymer" for-
mulation and totally unrelated to uv irradiation; or a decrease in recovery from the glass
surface as exposure time increased. Preliminary experiments exposing "polymeric" and
0
0 I 2 4 7
_1/
0 ] 2 4 7
y
0
•
1
"" •
2
•
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2,4-D D 2, 4-D 2, 4-D F
100 11 ~zg 110.5 #g 1105#g
~ • '41,
80 " P o ~ "'Polymer"
.y
60 ¢ " ,, ~°~" Conventional
o ,, Conventional s
J s
40 i/ 0 s
I
Conventional ~3
20 / o j
o J
Io I 09.o"
s
0 I I I __t
I | I __ t
0 1 2 4 7 0 1 2 4 7 0 1 2 4 7
Exposure time (hrs)
Fig. 3. Effect o f 356-nm uv irradiation (700 to 1 , 1 0 0 / a W / c m 2) on loss of conventional
and " p o l y m e r i c " 2,4-D and dicamba over a 7-day period.
Ultraviolet and Volatility Loss of Herbicides 283
conventional 2,4-D to 30°C dark conditions revealed no significant losses of either formu-
lation over a seven-day period4. Consequently, the rapid loss of "polymeric" 2,4-D noted
in Figures 3, D, E, F and 4 is interpreted as being caused by uv irradiation. Such rapid loss
may be caused by the "polymer" structure serving as a trap for uv photons whose energy
is transferred to the 2,4-D molecules in the "polymer" structure.
The resistance to uv loss noted for polymeric dicamba, relative to the conventional for-
mulation (Figure 3, B, C), may be a manifestation of increased resistance to temperature
degradation (or volatilization) that is imparted by the "polymerization" of this material.
That conventional dicamba is lost upon exposure to 30°C in the dark has been substanti-
ated by earlier work (Baur et al. 1973).
To provide further support for our contention that "polymeric" 2,4-D is rapidly de-
stroyed by long-wave uv irradiation, we incorporated a series of five industrial uv ab-
sorbers (Table I) at three different concentrations into both "polymeric" and conven-
tional formulations. The resulting solutions were given a six-hr exposure to long-wave uv
irradiation. The results of this experiment (Table II) indicate that two of the five
0 0
80 "Polymer"
/
"Polymer"
0
60 0 0
_o
O- 40 o/
20i/cove / ~ Co:ven~ion~
•
5 ~ w v
° - - L L...--I I ___ I I ~~ - - I I
0 2 4 6 8 10 12 0 2 4 6 8 10 12 0 2 4 6 8 10 12
Exposure time(days)
Fig. 4. Effect of 356-nm uv irradiation (700 to 1,100 #W/cm 2) on loss of conventional
and "polymeric" 2,4-D over a 12-hr period.
Conventional
80
,~ 60
o
~' 40 "'Polymer"
20 t "Polymer"~ ^ i o
n me r,W
Fig. 5. Effect of heat (60°C) on loss of conventional and "polymeric" 2,4-D over a
7-day period.
(Percent lost) a
Conventional RYLEX-H u 0 0 0
"polymer" 5 0 0
Conventional RYLEX-D 0 0 0
"polymer" 46 63 49
Conventional CYASORB-284 - 0 0 25
"polymer" 59 58 58
Conventional TINUVIN-328 - 8 5 3
"polymer" 21 39 48
Conventional None 0
"polymer" 60
(RYLEX-H and UVINUL D-50) provided excellent absorption at all rates without trans-
ferring the energy to the 2,4-D molecule. The remaining three resulted in no decrease in
loss of "polymeric" 2,4-D. CYASORB-284 (1.0%) appeared to cause some trapping and
energy transfer in the conventional formulation, resulting in a 25 percent loss. Minor
losses of conventional 2,4-D were noted for all rates of TINUVIN-328.
The ratio of molecules of uv absorbers to molecules of 2,4-D for the three absorber
rates was 10:1, 50:1, and 100:l for the 0.1, 0.5, and 1.0 percent solutions, respectively.
The data in Table II indicate that the rates of the effective absorbers were above the
levels needed to show a progressive increase in protective efficiency. The inclusion of the
absorbers had no effect on recovery or analytical efficiencies.
Earlier we provided evidence that the herbicide picloram was destroyed by long-wave
uv irradiation by way of a direct interaction of one photon with one molecule (Baur et al.
1973). The rapid loss of "polymeric" 2,4-D exposed to long-wave uv irradiation can be
interpreted as the result of loss by energy transfer, i.e., one photon of uv light resulting in
the degradation of more than one molecule of 2,4-D. This suggests that the "polymer"
structure acts as a trap for uv photons, whose energy is subsequently transferred to
several 2,4-D molecules within the "polymer."
O
--CH=CH-CH
The presence of the benzene ring should increase the uv absorption capacity relative to
O
II
a "polymer" produced using crotonaldehyde (CH3-CH=CH-CH) as the aldehydic com-
pontnet (Calvert and Pits 1967).
Volatilization studies. The purpose of the apparatus shown in Figures 1 and 2 was to
separate thermal losses into thermal degradation and volatilization. Each experiment in-
volved two separate conditions of exposure. A series of non-tubulated U-tubes (Figure 1,
point 5) containing 110.5 ~g of free acid dicamba coated on the internal surfaces were
capped and exposed for seven days to a 60 + I°C water bath. The difference between the
286 J . R . Baur and R. W. Bovey
amount of dicamba applied (110.5 #g) and the amount recovered is considered to consti-
tute thermal degradation loss.
The second condition involved applying 110.5 #g of dicamba to the internal surface of
a series of tubutated U-tubes exposed to the 60°C water bath (Figure 1, point 6). A
stream of N2, passed through these tubes, picked up volatilized dicamba and carried it to
a group of paired, tubulated U-tubes connected in series that were chilled to -32°C
(Figure 1, points 10 and 11). The volatile fraction was then condensed and deposited on
glass beads contained in the cold-trap U-tubes. The difference between the amount of
dicamba applied and the amount recovered from the 60°C flow tubes after a seven-day
period is considered to constitute the amount of dicamba lost by volatilization and
thermal degradation. The amount of dicamba recovered from the cold-trap U-tubes repre-
sents the fraction that was lost by volatilization.
The results of seven experiments given in Table IV show that conventional dicamba
undergoes thermal (37.9%), as well as volatility losses (60.1%).
The data for "polymeric" dicamba suggest that "polymerization" causes a reduction
in both thermal and volatility losses (21 and 46 percent, respectively) as compared to
37.9 percent (thermal) and 60.1 percent (volatility) losses noted for conventional
dicamba.
If the percent recovered by cold trapping is subtracted from the percent lost from the
60°C flow tubes, we find thermal degradative losses of 27.6 and 5.4 percent for conven-
tional and "polymeric" formulations of dicamba. These values are somewhat less than
those noted for the closed 60°C tubes. This discrepancy is reasonable in view of the fact
that the vapors present in the closed tubes were continuously exposed to 60°C and there-
(Percent lost) a
Conventional 0 2 4 6 13 2 5
Trans-cinnamatdehyde
"polymer" 0 24 42 53 57 38 55
Crotonaldehyde
"polymer" 0 21 38 40 43 53 49
fore could have undergone further thermal degradation, whereas vapors in the 60°C flow
tubes were constantly being removed and condensed in the cold-traps.
The efficiency of the apparatus with regard to "polymeric" dicamba was somewhat
less than that noted for conventional dicamba. Part of the discrepancy may be due to the
fact that fewer replicate samples of "polymeric" dicamba were examined. The experi-
mental procedure involved four experiments with ten tube replicates per experiment for
conventional dicamba; and three experiments comparing five tubes each of "polymeric"
and conventional dicamba. The tabular data (Table IV) reflect averages of all conven-
tional and all "polymeric" analyses.
The volatility of any solute is directly proportional to its vapor pressure. There are
several reports in the literature of herbicide materials that undergo volatilization, but yet
have widely varying vapor-pressure values. For example, the vapor pressures of the vola-
tile herbicides trifluralin and dichlobenil are 1.99 × 10-4 mm Hg at 29.5°C and 5.5 ×
10-4 mm Hg at 20°C, respectively (Ashton and Crafts 1973). Atrazine, on the other
hand, reported to be affected by volatility losses (Walker 1972), has a vapor pressure
value of 3 × 10-7 mm Hg at 25°C (Ashton and Crafts 1973). That dicamba would ex-
hibit some volatility is reasonable in that its vapor pressure (2 × 10-5 mm Hg at 25°CS)
falls midway between those reported for trifluralin and atrazine, both of which show
volatility losses.
Extrapolation of the foregoing data to actual field conditions without the benefit of
further experimentation may not be valid. These experiments were conducted under
laboratory conditions standardized for the purpose of comparing "polymeric" and con-
ventional formulations of two common herbicides. There is no evidence to assume that
losses due to volatilization, thermal, and uv degradation from a glass surface under
laboratory conditions will be the same from leaf and soil surfaces under field conditions.
Percent
Conventional a 37.9 87.7 60.1
These data are presented to provide a basis for similar studies under field conditions.
Now that we know the "absolute" effects, we are in a position to see how they are
altered by the natural environment.
References
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