COPPER FUNGICIDES.

By SPENCER TJMFREVILLE PICKERING, M.A., F.RS.

INVESTIGATIONS on the various products of the action of lime on

copper sulphate1, including ordinary Bordeaux mixture, led to the
conclusion that the efficacy of such substances as fungicides depended
on the proportion of copper in them which is rendered soluble by the
carbon dioxide of the air, and, that if a deficiency of lime is used to
start with, one of the lower basic sulphates of copper is obtained, from
which carbon dioxide liberates a much larger proportion of copper
than it does from the more highly basic sulphates present in ordinary
Bordeaux mixture. The lowest basic sulphate is, owing to its physical
condition, unsuitable for spraying purposes; but this is not so with the
compound 10 CuO, SO», obtained by adding lime-water to copper
sulphate just short of alkalinity, and this substance has been put on
the market under the name of Woburn Bordeaux Paste. In the
absence of secondary reactions, carbon dioxide should convert one-tenth
of the copper present in it into soluble copper sulphate, 2 (10 CuO, SOa)
+ 9 COj = 9 (2 CuO, COS) + 2 CuSO4, whereas with ordinary Bordeaux
mixture, any copper sulphate formed in this way, would be decomposed
by the excess of lime present, and that ultimately remaining undecom-
posed would be very small in amount. Direct experiments led to the
conclusion that under the action of carbon dioxide the proportion of
copper rendered soluble from Woburn Bordeaux was 18 to 20 times
greater than that from ordinary Bordeaux, and this ratio was found to
agree with the relative energy with which the two substances scorched
foliage, as well as with their behaviour in other respects. At the same
time it was pointed out that under the conditions obtaining in practical
spraying, such a proportion might not obtain, and, pending further
1
Eleventh Report of the Woburn Experimental Fruit Farm, 1910; this Journal, m. 171;
Trans. Chan. Soc. 1907, 1908, afid 1909, 1411.
Jonrn. of Agrio. Soi. rv 19
274 Copper Fungicides
direct trials, it was recommended that the proportion of Wobum
Bordeaux should not be reduced below one-twelfth of that of ordinary
Bordeaux. Recent experiments have indicated that even this propor-
tion is too small, one-sixth being, apparently, the equivalent proportion,
i.e. ordinary Bordeaux is equivalent in its fungicidal action to Woburn
Bordeaux containing only one-sixth as much copper.
The evidence on which this proportion is based will not be discussed
in the present communication, but only the principles underlying the
difference in potency of the two substances.
Gimingham and Barker1 question the validity of the principle that
solubility of the copper compound is essential in order that it may
exert its fungicidal action, and doubt that such solubility is brought
about by the action of carbon dioxide, suggesting that mere contact
between the fungus and an insoluble copper compound is sufficient to
account for fungicidal action. They show, in the first place, that if
air, instead of carbon dioxide, is passed through a liquid containing the
basic sulphates, only a very small, instead of a large, proportion of the
copper becomes soluble, and that if the comparatively strong copper
solution obtained by the action of carbon dioxide is exposed to air,
nearly all of the copper becomes deposited2. This latter fact was
repeatedly noticed by the present writer, and it was certainly an
omission on his part that it did not lead him to differentiate between
the action of carbon dioxide and of ordinary air on these compounds.
But it is questionable how far such a differentiation is of importance,
from the point of view of practical spraying, for any fluid sprayed on to
the leaves of trees will soon find itself bathed in an atmosphere of
the carbon dioxide evolved from the leaves themselves.
Gimingham further questions whether the carbon dioxide in air can
reuder soluble any, or more than mere traces of the copper in ordinary
Bordeaux mixture. He seems, however, to have overlooked a very
simple experiment which places this point beyond dispute, namely,
that when a drop of Bordeaux mixture is placed on a piece of paper
impregnated with potassium ferrocyanide, as soon as it dries up, and
communication between the excess of lime and the particles of basic
1
This Journal, rv. 69 and 76.
s
Throughout his paper, Gimingham speaks of the amount of copper remaining in
solution in this and other similar cases, as nil. This simply means that it was less than
that recognisable by the ordinary ferrocyanide test on which he relied. As will be shown
below, the action of the liquids on iron would have proved that there was copper still in
solution; and the ferrocyanide test would have done the same, if the liquids bad been oon-
centrated by evaporation.
 S. U. PICKERING 275

sulphate is thereby prevented, the red colour of copper ferrocyanide

makes its appearance.
This experiment may be modified so as to give simple and incon-
trovertible evidence that it is the carbon dioxide in the air which
renders the copper in Bordeaux mixture soluble. Into two similar
tubes, pieces of ferrocyanide paper with a drop of Bordeaux mixture on
them are introduced: a current of air is then drawn through the tubes,
this air being deprived of its carbon dioxide before entering the second
one: the paper in this tube remains unaltered in colour, whilst that in
the first tube becomes red in a few minutes.
It may also be added that the invariable presence of dissolved
copper in the drip-water collected from trees sprayed with Bordeaux
mixture has been fully established by Crandall1, though in this case
solvent agencies other than the carbon dioxide of the air were not
excluded.
No doubt, the actual copper contents of any solution obtained by
the action of air on Bordeaux mixture may be very small, but Barker
and Gimingham do not seem to have realised the extent to which even
such very dilute solutions may operate, when brought into contact
with any substance which can utilise and remove the copper as soon as
it passes into solution. Some of the simple experiments quoted below
will give striking illustrations of this.
In the second paper alluded to, Barker and Gimingham seek to
prove that the solvent of normally insoluble copper compound is a
substance excreted by the fungus itself. That fungus spores while
germinating, and during growth, excrete a substance capable of acting
on the cell walls of the host plant, cannot be doubted, and that this
substance may be capable of dissolving copper compounds was freely
admitted (Eleventh Woburn Report, p. 107); but it seems impossible
to attribute any such excretive action to dormant spores, without
applying a novel meaning to the word " dormant." Whether, however,
it is dormant or active spores which are in question, the excretion of a
solvent substance from them could only be established by examining
their action on a copper compound which is really insoluble in water,
and this Barker and Gimingham have not done; for all their experiments
have been performed with 10 CuO, SO8, which is not insoluble. As
-clearly indicated by the present writer, although this compound does
not dissolve sufficiently to give a reaction with ferrocyanide by testing
1
Bulletin No. 135 of the University of Illinois Agricultural Experiment Station.
19—2
276 Copper Fungicides
in the ordinary way, it does dissolve suflSciently to react with iron, and
this reaction soon becomes very considerable: in fact, so far are Barker
and Gimingharri's experiments from establishing the excretion of
solvent matter from fungus spores, that they would have obtained
exactly the same, or strictly similar, results, had they substituted a
piece of metallic iron for the spores in question.
In the following experiments a current of air or other gas was
passed at the rate of 8 litres an hour through 225 c.c. of liquid con-
taining 0'375 grams of copper in the form of one of the basic sulphates,
and in the liquid were placed two bright iron rods, weighing together
about 30 grams, and presenting a surface of 28 sq. cm. to the liquid.
These were removed at intervals, and weighed, any deposit of copper
on them being rubbed off with a cloth. The loss in weight of the rods
gave, of course, the amount of copper abstracted from the liquid. In
duplicate experiments this loss was fairly constant1, but not sufficiently
so to be trustworthy; consequently, two determinations, and only two,
were always made at the same time in. the same current of gas, one of
these being used as the standard of comparison, and this was always
one in which the copper was present in the form of 10 CuO, SO3, made
by.adding lime-water to the normal sulphate just short of alkalinity.
In illustration of the character of the action the following results
with 10 CuO, SO8 may be quoted, the apparent loss in weight of the
iron being translated into its equivalent of copper, and expressed as a
percentage of the total copper originally suspended as basic sulphate
in the liquid.
1. After 10 hours ... .. 10 '9 per cent, copper removed
2. After 10 hours more 7-0 ,, more copper removed
3. ,1 * 1 J, 6-4
4. I > . 3-6 ,
5. ,t » , 2-0 ,
6. ) ) , 1-7
7. ,> i . 75 ,
8. » J . 43
9.. ,i > . 8-6
10. ,j > , 7-5
11. ,j i , 4-5
12. ,i J
, 2-6
Thus, during the first 10 hours, 10*9 per cent, of the copper was
removed; but the rate of removal decreased rapidly down to 1"7 per
1
In Beven cases the copper equivalent of the iron dissolved in 3 hrs, varied from 3'5 to
4-7 per cent., with a mean of 4-2,
 S. U. PICKERING 277
cent, per 10 hours after 50 hours had elapsed; this decrease, however,
is mainly due to the. iron becoming covered with an irremovable
coating of copper or iron oxide, for on substituting fresh bright pieces
of iron for the first ones, as was done after the 6th and 8th observations,
the original rapid rate of action was nearly restored. If the iron could
be kept permanently bright, this rate of action would be maintained-,
and, indeed, would be greater than any of the values entered above;
for during the first hour alone it amounted to 15 per cent. At that
rate it would require only 70 hours to remove the whole of the copper
present: and this is the case, be it noted, with a substance which
dissolves to a smaller extent than "00005 gram of copper in 100 c.c.
The loss in weight of the iron, however, in these experiments may
give a somewhat exaggerated estimate of the amount of copper removed,
at any rate, when the action has proceeded for some time, since a
secondary reaction occurs, as previously mentioned, the metallic copper
and iron forming a couple which electrolyses the liquid, producing
hydrogen and iron oxide.
The relative action of air on the various copper compounds is
sufficiently illustrated by the following values obtained after three
hours, though confirmatory results were also obtained after both shorter
and longer intervals.
2-5(4CuO, SO,) 10CuO,SOs IOCUO, SO,, 8OaO 5(2OuO, COjj
Per oent. copper removed 7-3 . 4-2 2-3 1-0
Belative values 174 100 54 23

The sulphate, 4 CuO, SO8, is the least basic one obtained by the
action of lime on copper sulphate, and is more soluble than 10 CuO, SQ,
whilst 10 CuO, SO8, 3CaO, is the most basic one, and is that present,
together with excess of lime, in ordinary Bordeaux" mixture; it is
strongly alkaline, and insoluble, and does not itself act on ironj but as
soon as carbon dioxide is passed into the liquid containing it, it begins
to be decomposed with the formation of 10 CuO, SO,, and the mixture,
though still alkaline, acts on the iron at the rate indicated. Ordinary
copper carbonate, as will be seen, exercises only one-quarter as energetic
an action as the sulphate 10 CuO, SO8 (quantities containing equal
weights of copper being compared), and in some cases the action with
the carbonate was found to be much more feeble than that in the
experiment here recorded. ' :
When ordinary Bordeaux mixture itself was examined in this way,
taking a mixture made from equal weights of crystallized sulphate and
278 Copper Fungicides
calcium oxide, the iron remained perfectly bright in it till the current
of air had been passed through it for 130 hours; then, all the free lime
having been carbonated1, the basic sulphate began to be attacked, and
the iron was soon acted upon at the rate indicated above for 10 CuO, SO,,
3CaO.
A simple experiment of this sort must place it beyond doubt that
the copper in Bordeaux mixture is brought into the soluble condition
by the action of air, and the greater the excess of lime present, the
longer is the interval before this action commences, though in practical
spraying it will always be much shorter than in this experiment, owing
to the deposit drying up and isolating the particles of basic sulphate
from those of lime.
The following experiments with Woburn Bordeaux (10 CuO, SO8),
confirm the writer's previous results as to the great increase of the
action produced by an atmosphere of carbon dioxide, but they show, at
the same time, that the action is actually reduced by carbon dioxide
until this latter reaches a certain proportion. Except in the last
experiment, the results were obtained by drawing the air charged with
carbon dioxide, first through a bottle containing the basic sulphate, next
through apparatus capable of absorbing this gas, and then through a
second bottle with basic sulphate. In the last experiment, where
carbon dioxide itself was used, the two bottles had to be separate, the
rates of it, in the one case, and of the air, in the other, being adjusted
so as to be as nearly the same as possible. In the third experiment the
proportion of carbon dioxide was not determined, the air being drawn
from a funnel suspended over a burning candle. The results refer to
observations made after 3 hours' passage of the gas.

Air Air with Air with Air with

containing •03 per cent. x per cent. 10 per cent. OOj
noCO2 CO, 00 2 COa only
Relative action... 109 100 38 58 834

Thus by depriving the air of its carbon dioxide the action is

increased by 9 per cent., and by increasing the proportion of carbon
dioxide to a certain extent the action is reduced, though what the
minimum point is, and what proportion of carbon dioxide produces it,
has not been determined. A further increase in the proportion of the
gas then increases the reaction till, with the undiluted gas, the action
is more than eight times as rapid as with ordinary air.
1
The total air used contained about twice as mnch carbon dioxide as that required
by the lime, but the current was much to9 rapid for it all to be utilised.
 S. U. PICKERING 279
As bearing on the question of the nature of the chemical reaction
occurring in this case, the influence of the presence of calcium sulphate
on the amount of copper rendered soluble by carbon dioxide must be
borne in mind. According to the equation given above this gas
should render soluble only 10 per cent, of the total copper present, but
experiments generally indicated as much as 50 per cent, passing into
solution (Eleventh Woburn Report, pp. 31, 63), and this was traced
mainly to the presence of the calcium sulphate resulting from the
action of the lime on the copper sulphate originally taken. The
influence of this calcium sulphate is further illustrated by the following
experiments with iron, where in the case of A the precipitate of basic
sulphate was washed free from admixed calcium sulphate1, in that of B
it was not so washed, and in that of C an extra equivalent of calcium
sulphate was added.
A, B, 0,
No 9CaSO4to 18CaSO t to
CaSO4 each 10 Cu each 10 Cu
Relative aotion, 3 hours 79 100 121

A similar experiment with copper carbonate showed that in that

case the presence of calcium sulphate had a still greater effect, increas-
ing the action six-fold (D and E, below), and rendering such a mixture
three-quarters as effective as Woburn Bordeaux itself (B); whereas
calcium chloride (F) only doubled the action, and calcium carbonate (G)
produced no effect at all.
5(CuCOs,CnO) with
10 CnO, SO, NH 20CaSO4 20CaCla j
B, D, E, F, G,
Relative aotion... 100 12 76 28 12

An exact analysis of the chemical reactions involved in the above

results would probably be a tedious matter, but they do not appear to
present any fundamental difficulties. The basic sulphate 10 CuO, SO,
is itself soluble in water, and, hence, acts on iron: the first action of
carbon dioxide upon it is probably to produce a compound composed of
a basic sulphate with basic carbonate, similar to that obtained by
precipitating copper sulphate with acid sodium carbonate (Chem. Soc.
Trans. 1909, 1415), and if this is less soluble than the original basic
sulphate, the reduction in the action of iron would be accounted for.
1
Some calcium sulphate is always retained by the basic sulphate in a state of
combination (he. tit. p. 49).
9
It would, of course, owing to its physical condition, be much less effective as a spray-
fluid in practice.
280 Copper Fungicides
A further increase in the proportion of carbon dioxide would convert the
basic into the normal carbonate, and this would probably form with
copper sulphate a cupricompound, exhibiting, as such cupricompounds
do, a relatively great solubility, which would account for the great
increase in activity as regards iron. Many cupricarbonates have been
obtained (he. cit. 1911, 99, 800) which may be regarded as containing
the elements of CuCO, with those of some other carbonate, and, as was
pointed out at the time, a sulphate or other salt might probably be
substituted for one or other of the carbonates: since then several
substances of that sort have been obtained. The formation of these
will also explain the increased activity produced by the addition of
calcium sulphate, either to the basic sulphate or carbonate of copper.
The values given on p. 277 show that in spite of the small solubility
of IOCUO, SO, the greater part of the copper in it may pass into
solution and be utilised within a comparatively short time, provided
there is any body present, such as iron, to react with it and remove it
from the solution. This will occur equally if it be removed by absorp-
tion into a fungus spore or the leaf of a plant, and the absorption in
that case should be at a much greater rate than in these experiments,
because the reacting surface exposed to a given amount of copper would
be far greater. The relative action with 1, 2 and 10 iron rods in
liquids containing the same amount of basic sulphate was found to be
1 rod 2 rods 10 rods
Relative action... 114 2x100 10x72

or a reduction of 40 per cent, per unit area exposed when the actual
area was increased ten fold. But rough calculation shows that the
same amount of copper used in these experiments, when sprayed on to
a tree would be spread over a surface 6000 times greater in area than
that of the one iron rod, and, even if the rate of action were thereby
reduced to only one-hundredth of that observed in the case of the one
rod, the actual amount of action occurring in unit time would be sixty
times greater than with the rod. Thus we may get a very energetic
absorption or fungicidal action, with a substance showing a minimum of
solubility, though the possibility of this action depends entirely on the
substance passing into solution. Of course, if the solid basic sulphate
is separated from the liquid, the latter by itself will give no appreciable
reaction with iron, just as Barker and Gimingham found that it had
but little action on fungi, simply because there is very little copper in
solution, but the fact that the presence of the solid sulphate in the
 S. U. PICKERING 281
liquid is necessary for the production of an appreciable action in either
case, is certainly no proof that the solid is directly acted upon either by
the iron or the fungus; the solid merely serves to keep up the supply
of dissolved copper in the liquid.
The experiment which Barker and Gimingham rely upon as estab-
lishing definitely their view that an insoluble copper compound is
dissolved by excretion from the fungus, appears to be very unconvincing.
A drop of basic sulphate liquid on a cover-slip was dried; a drop of
liquid containing fungus spores was similarly dried on another slip, and
partially superimposed on the patch of basic sulphate. The slips were
then kept in a moist atmosphere for 24 hours, and it was found that
the spores had germinated only in the region where there was no basic
sulphate. It is difficult to see wherein the convincingness of this result
lies: for it is just what would occur if the fungicidal action were due to
the presence of soluble copper in the fungicide. That the result affords
no proof of the excretion of a solvent substance from the spores, may
be demonstrated by substituting for these a substance which certainly
excretes no copper-dissolving body, namely, potassium ferrocyanide:
a drop of a solution of this and of Woburn Bordeaux mixture are dried
on separate pieces of paper, they are then partially superimposed, and
pressed together, being kept moist by placing above them a slightly
damped piece of paper. After a time the portions of the blotches which
were in contact become red, whilst those portions which were not in
contact remain unaffected. No action occurs if the papers are kept
quite dry.
It is only necessary to add that if fungicidal action depended on a
solvent material exuded from the fungus, all copper compounds, or at
any rate all the basic sulphates and carbonates, would be equally
efficacious for a given weight of copper present, a proposition which is
contrary to all experience. Indeed ordinary Bordeaux mixture with
excess of lime should be much more effective than other compounds
with the same copper content, for the lime itself seems to have a con-
spicuous fungicidal action (Freeman, this Journal, in. 400); and this
fungicidal action, it may be remarked, accounts for the results obtained
by Barker and Gimingham (loc. cit. p. 86), when they found that
ordinary Bordeaux was effective in an atmosphere free from carbon
dioxide, which they accept as proving that carbon dioxide does not
bring the copper of such a mixture into solution.