Maria Lodovica Gullino, Federico Tinivella, and
Angelo Garibaldi
This feature reviews the broad-spectrum fungicide mancozeb.
Introduced in 1962, it still plays a significant role in the world
fungicide market. Mancozeb possesses a number of key attributes
that have contributed toward its development into a globally impor-
tant tool in modern chemical-based plant disease management.
These attributes are discussed from the perspective of both public
and private research.
History and Role of Mancozeb in Disease Management
Dithiocarbamate development. For a review of the develop-
ment of mancozeb, it is useful to review the history of the develop-
ment of the dithiocarbamates as a group. McCallan (119) produced
an excellent review of this class of products at a time when they
were becoming established as key tools for the management of
plant diseases. Dithiocarbamate-type compounds were originally
used as accelerators in the rubber vulcanization process (119). The
first derivative of a dithiocarbamate to achieve prominence as a
fungicide was tetramethylthiuram disulfide, more commonly
known as thiram, for which a patent was granted in 1934 (200).
Thiram was demonstrated to be an effective seed dressing by
Muskett and Colhoun (145), and Harrington (77) demonstrated
thiram’s utility for control of turf diseases. Thiram was not a par-
ticularly strong product when applied as a foliar spray, and the next
generation of more active molecules based on metal salts of dithio-
carbamic acid was soon to appear. Ferric dimethyl dithiocarbamate
(ferbam) was first reported by Anderson (6) and independently by
Kincaid (101). It gave good control of orchard diseases and gained
wide acceptance as a spray for ornamentals due, in part, to the fact
that its potential for phytotoxicity was significantly less than those
of copper or sulfur sprays. Following ferbam was the closely re-
lated ziram (zinc dimethyldithiocarbamate), which was found to be
more useful on vegetable crops (80,211).
The first dithiocarbamates were prepared from a monoamine and
carbon disulfide. In 1940, W. F. Hester of Rohm and Haas, Inc.,
prepared a dithiocarbamate from a diamine. Hester’s compound,
disodium ethylene bisdithiocarbamate (nabam), can be considered
the first true ethylene bisdithiocarbamate (EBDC). A patent was
awarded on the compound in 1943, and the first published scien-
tific report appeared in print in the same year (46). Nabam was
unstable as a solid and had to be used in liquid form. Thirteen
years after its introduction, it was demonstrated that nabam was
Corresponding author: M. L. Gullino, Agroinnova, University of Torino, Via
Leonardo da Vinci, 44, 100095 Grugliasco, Turin, Italy;
E-mail: marialodovica.gullino@unito.it
doi:10.1094 / PDIS-94-9-1076
© 2010 The American Phytopathological Society
1076 Plant Disease / Vol. 94 No. 9
Agroinnova, University of Torino, Turin, Italy
Gregory M. Kemmitt
Dow AgroSciences, European Development Center,
Abingdon, Oxfordshire, UK
Leonardo Bacci
Dow AgroSciences Italia srl, Bologna, Italy
Brian Sheppard
Dow AgroSciences, Punta Gorda, FL 33950, USA
not fungicidal in itself, and only when the compound was exposed
to the air and converted into a fungitoxic active compound did it
exhibit fungitoxicity. Nabam’s high water solubility and relative
instability meant that performance was somewhat variable (26).
Heuberger and Manns (79) discovered that adding zinc sulfate to
the spray tank had a stabilizing effect on the nabam. The new liq-
uid product was commercialized in 1944 and given the trade name
Dithane D-14 (26). From this point forward, utilization of the com-
pound by growers accelerated rapidly, and it became widely
adopted for management of many vegetable diseases and gained
particular popularity with potato growers in the United States,
where it rapidly replaced Bordeaux mixture. The reaction product
that formed in the spray tank when zinc sulfate was added to na-
bam was zinc ethylene bisdithiocarbamate (zineb). Field tests in
1945 showed zineb to be a stable and superior fungicide, and it was
rapidly commercialized under the trade name Dithane Z-78. In
1947, national cooperative potato fungicide trials were organized
in the United States and tested over a 3-year period. In these stud-
ies, nabam and zineb consistently proved their efficacy for control
of late blight caused by Phytophthora infestans and early blight
caused by Alternaria solani on potato. In the following decade,
nabam and zineb were rapidly adopted by growers in a wide range
of crops. By 1953, the two products combined were being used on
75% of the total U.S. potato hectarage (26). Other significant U.S.
uses were on tomatoes, onions, carrots, cucurbits, celery, hops,
spinach, beets, beans, peppers, tobacco, cherries, sweet corn, and
pecans. In Europe, zineb became well established for control of
grape downy mildew (Plasmopara viticola) and apple scab (Ven-
turia inaequalis). In 1952, Rohm and Haas started to operate a
commercial plant in France for the manufacture of Dithane.
The development of new EBDCs continued apace, and DuPont
was granted a patent for manganese ethylene bisdithiocarbamate
(maneb) in 1950 (61). Maneb was more active than nabam or zineb
and raised the bar for performance yet further. In 1962, Rohm and
Haas registered the zinc ion complex of maneb (mancozeb), which
was to become the most important and commercially significant of
all the EBDCs. Two further alkylene bisdithiocarbamate fungicides
were also developed at around the same time as mancozeb. Pro-
pineb was first reported in 1963, and metiram was first introduced
into Germany by BASF around 1958 (201). By the mid-1960s, the
EBDC fungicides were considered to be the most important and
versatile group of organic fungicides yet discovered (119). This
situation led to the development of mancozeb. In the intervening 46
years since commercialization, mancozeb has been developed in
over 70 crops for the control of numerous fungal plant pathogens.
Key representative uses for mancozeb spectrum and utility are
found across a cosmopolitan range of plant groups and fungal dis-
eases (Table 1). This theme will be discussed in more detail later in
this paper. As a successful commodity product, mancozeb is cur-
rently produced by numerous manufacturers around the world.
Dow AgroSciences (DAS) operates as the leading registrant and Mode of Action and Spectrum of Activity
producer following its acquisition of the molecule with its purchase Chemistry and biochemical mode of action. Mancozeb [[1,2-
of the Rohm and Haas agrochemical business in 2001. Mancozeb ethanediylbis]carbamodithioate]](2-)]manganese mixture with
has become an internationally traded product, and DAS currently [[1,2-ethanediylbis[carbamodithioate]](2-)zinc belongs to the di-
supports registrations and uses for mancozeb in almost 120 coun- thiocarbamate grouping of fungicides and more specifically to the
tries worldwide. Until 2004, mancozeb was the primary fungicidal class of compounds known as ethylene bisdithiocarbamates
active ingredient as measured by total annual sales (48). In 2007, (EBDCs). This group of compounds also includes mancozeb’s close
global sales were around US$500 million, second only to tebu- relatives: maneb, metiram, propineb, and zineb (Fig. 1). Mancozeb
conazole with $525 million (48). If we consider the value of sales
of co-formulations of mancozeb with other fungicides, this figure
rises to approximately $740 million in 2007 (48). During a long `
history of commercialization and continuous development, numer-
ous different formulations of mancozeb have been developed for
specific crop uses and markets around the world. Although use of
mancozeb alone is still significant, around 33% of the active ingre-
dient sold in 2007 was applied in co-formulation with another
active ingredient, usually a systemic single-site inhibitor, e.g., me-
fenoxam. Mancozeb is typically included in these mixtures as a
tool to help with resistance management and to broaden the spec-
trum of the product. Representative examples of key mancozeb
mixture partners include benalaxyl, benalaxyl M (kiralaxyl), ben-
thiavalicarb, copper, cymoxanil, dimethomorph, famoxadone, fena-
midone, folpet, fenbuconazole, fosetyl-aluminum, iprovalicarb,
mandipropamid, mefenoxam, metalaxyl, myclobutanil, sulfur, and
zoxamide.

Table 1. Key representative uses of mancozeb

Crop Major disease Pathogen controlled
Potato Early blight Alternaria solani
Late blight Phytophthora infestans
Tomato Early blight Alternaria solani
Late blight Phytophthora infestans
Leaf spot Septoria lycopersici
Leaf mold Cladosporium fulvum
Anthracnose Colletotrichum coccodes
Bacterial speck Pseudomonas syringae
and spot Xanthomonas campestris
Grapevine Downy mildew Plasmopara viticola
Black rot Guignardia bidwellii
Rotbrenner Pseudopezicula tracheiphila
Phomopsis Phomopsis viticola
Citrus Anthracnose Colletotrichum spp.
Black spot Guignardia citricarpa
Melanose Diaporthe citri
Brown rot Phytophthora spp.
Pome fruit Scab Venturia inaequalis
Banana Black sigatoka Mycosphaerella fijiensis
Cucurbits Downy mildew Pseudoperonospora cubensis
Anthracnose Colletotrichum orbiculare
Alternaria Alternaria alternata
Gummy stem blight Didymella bryoniae
Bacterial diseases Xanthomonas campestris pv.
cucurbitae, Pseudomonas
syringae
Lettuce Downy mildew Bremia lactucae
Onions Downy mildew Peronospora destructor
Gray mold Botrytis squamosa
Stone fruit Rust Tranzschelia discolor
Corn Rust Puccinia sorghi
Helminthosporium Helminthosporium maydis
leaf blight
Crucifers Downy mildew Peronospora parasitica
Wheat Leaf spot Mycosphaerella graminicola
Mangoes Anthracnose Colletotrichum gloeosporioides
Peanuts Cercospora leaf spot Cercospora arachidicola
Sugarbeet Cercospora leaf spot Cercospora beticola
Turf and Multiple diseases
ornamentals
Fig. 1. Structural formula of mancozeb and related compounds.

Plant Disease / September 2010 1077

is classified by the Fungicide Resistance Action Committee
(FRAC) in mode-of-action group M (Multi Site Action). Mancozeb
itself is not fungicidal and can effectively be considered a pro-
fungicide which, when exposed to water, breaks down to release
ethylene bisisothiocyanate sulfide (EBIS), which is then converted
via the action of UV light into ethylene bisisothiocyanate (EBI).
Both EBIS and EBI are believed to be the active toxicants and are
thought to interfere with enzymes containing sulphydryl groups.
This fatal disruption of core enzymatic processes is postulated to
inhibit or interfere with at least six different biochemical processes
within the fungal cell cytoplasm and mitochondria (92,113).
Biological activity. The direct effect of mancozeb upon core
biochemical processes within the fungus results in inhibition of
spore germination (195,210,213). Mancozeb displays the charac-
teristics of a typical multi-site protectant-only fungicide, in that
following application onto the target plant, the compound remains
on the leaf surface and does not penetrate through the cuticle to
where systemic redistribution can occur (91). This is clearly impor-
tant because penetration of a general toxophore such as mancozeb
into plant cells would likely cause phytotoxicity. Fortunately, man-
cozeb has an excellent record of crop safety over a wide range of
crops and environmental conditions. Mancozeb does not show
curative properties when sprayed onto plants where disease has
already established. It is assumed this is due to the fact that disease
is already established inside the plant tissue where mancozeb can-
not penetrate.
The rate of breakdown of mancozeb into EBIS and EBI can di-
rectly affect the residual activity of the compound on plant foliage.
Each mancozeb particle consists of a zinc-rich shell surrounding a
central nucleus of polymer-structured EBDC. This structure is
extremely stable, and the low solubility of the zinc shell means
EBDC can pass through this layer and be deposited on the leaf

Table 2. Effectiveness (%) of mancozeb applied alone for the control of key pathogens on different crops
Phylum/ Dose Effectiveness
Kingdom Pathogen Crop (g a.i./ha) (%)a Reference
Oomycetes Peronospora destructor Onion (Allium cepa L.) 400-5,600 50 ± 32 43, 86, 162, 186
Albugo cruciferarum Mustard (Brassica juncea L.) 2,000 83 189
Peronospora parasitica Rocket (Eruca sativa L.) 1,280 97 131
Pseudoperonospora cubensis Melon (Cucumis melo L.) 1,600 62 ± 21 11, 100, 116
Pseudoperonospora cubensis Cucumber (Cucumis sativus L.) 1,600 50 ± 2 135
Pseudoperonospora cubensis Luffa vine (Luffa acutangula L.) 1,125-2,500 53 ± 18 93
Phytophthora cactorum Apple (Malus spp.) 2,240 60 ± 17 158
Phytophthora fragariae Strawberry (Fragaria × ananassa) 4,000-8,000 46 ± 31 140
Bremia lactucae Lettuce (Lactuca sativa L.) 1,440-1,600 52 ± 41 62, 209
Phytophthora vignae Chick-pea (Cicer arietinum L.) 1,440 50 59
Phytophthora infestans Potato (Solanum tuberosum L.) 1,360-3,000 73 ± 22 7, 23, 39, 57, 134, 146,
192
Phytophthora infestans Tomato (Solanum lycopersicum L.) 2,500-3,000 61 ± 26 13, 66, 152, 202
Plasmopara viticola Vine (Vitis vinifera L.) 800-3,600 79 ± 22 1, 7, 8, 31, 40, 47, 51, 52,
53, 54, 65, 75, 114, 136,
137, 138, 139, 143, 156,
157, 160, 167, 208
Peronospora belbahrii Basil (Ocimum basilicum L.) 1,600 54 ± 10 133
Peronospora sparsa Rose (Rosa spp.) 1,440 11 151
Ascomycetes Guignardia citricarpa Orange (Citrus sinensis L.) 1,600-2,400 64 ± 30 41, 170, 171
Claviceps africana Sorghum (Sorghum vulgare L.) 1,500 68 164
Podosphaera xanthii Watermelon 2,550 41 ± 14 98
(Citrullus lanatus Thunb.)
Didymella bryoniae Watermelon 2,520 33 ± 31 84, 97, 168
Didymella bryoniae Melon 1,400 87 ± 10 100, 168
Taphrina deformans Peach (Prunus persica L.) 1,600-2,500 75 ± 16 122, 175, 196
Venturia inaequalis Apple 2,500-5,200 66 ± 20 9, 55, 104, 105, 150, 172,
203, 215
Gloeodes pomigena and Apple 3,554 67 9, 29
Zygophiala jamaicensis
Botryosphaeria obtusa Apple 3,554 40 9, 29
Aureobasidium pullulans Pear (Pyrus spp.) 3,400 47 ± 21 193
Microdochium panattoniana Lettuce 500-1,400 65 ± 39 153
Mycosphaerella arachidis Peanut (Arachis hypogaea L.) 2,000 46 165
Heterosporium echinulatum Carnation (Dianthus spp.) 1,600 73 ± 27 159
Deuteromycetes Alternaria spp. Tangelo (Citrus tangelo, C. reticulata 1,600 93 ± 4 194
Blanco × C. paradisi Macf.)
Botrytis spp. Onion 2,240 68 107, 111
Alternaria porri Onion 2,500 44 ± 19 107, 174, 188
Stemphylium vesicarium Onion 2,500 52 ± 27 76
Alternaria porri Leek (Allium porrum L.) 2,500 95 74
Stemphylium vesicarium Asparagus (Asparagus officinalis L.) 1,700 88 ± 5 124
Alternaria brassicae Mustard 2,000 39 ± 11 121, 176, 180
Alternaria brassicae Cabbage (Brassica oleracea L.) 2,000 50 ± 27 181
Alternaria dauci Carrot (Daucus carota L.) 2,000 38 ± 17 14, 15
Septoria apiicola Celery (Apium graveolens L.) 1,600 88 ± 13 3
Septoria spp. Wheat (Triticum aestivum L.) 1,500-1,600 58 ± 46 37, 112, 130, 204
Fusarium graminearum Wheat 1,680 18 ± 5 89, 129
Bipolaris oryzae Rice (Oryza spp.) 1,120 21 154
(Continued on next page)
a Expressed as Abbot’s index: (Control index – treatment index)/control index.

1078 Plant Disease / Vol. 94 No. 9

surface at a controlled rate. This controlled release helps to regu-
late the duration of fungicidal efficacy and improve foliar residual-
ity. In order to provide effective control, a continual barrier of man-
cozeb must be present on the leaf surface. This barrier is threatened
because it is constantly being diluted by the effects of weathering
as well as the plant producing new unprotected growth.
Spectrum of activity. The multi-site nature of mancozeb’s mode
of action means that it has demonstrated activity against a wide
range of fungi including ascomycetes, oomycetes, basidiomycetes,
and imperfect fungi. Nearly five decades of use and continual de-
velopment have led to registrations and claims of efficacy in over
70 crops and 400 different diseases (109). The compound’s broad
spectrum of activity is a key contributor to its commercial success,
and this aspect is worthy of further analysis. In preparation for this
paper, a bibliographic search was undertaken looking for disease
control data reported for mancozeb in different pathosystems. This
search encompassed hundreds of papers published during the pe-
riod 1980 to 2007. A summary of crops, pathogens, and a guide to
overall efficacy resulting from the literature search was produced
(Table 2). Effectiveness is scored as Abbot’s index (%), derived
from rates expressing disease incidence and/or severity or, when
this is not available, crop yield. Generally, mancozeb effectiveness
is higher if the product is applied at an early infection stage. The
descriptions of activity within various plant groupings are not ex-
haustive, and the reference to use rates are not necessarily repre-
sentative of all possible use patterns and labels for mancozeb
within a global context. The table is a brief distillation of the large
body of available literature on mancozeb efficacy and seeks to
convey to the reader an idea of the scale and breadth of mancozeb
utility as a broad-spectrum fungicide.
The majority of mancozeb uses are foliar applications; however,
the compound also has utility as a seed treatment and as a fungi-

Table 2. (continued from previous page)

Phylum/ Dose Effectiveness
Kingdom Pathogen Crop (g a.i./ha) (%)a Reference
Pyricularia oryzae Rice 1,400 28 179
Exserohilum turcicum Corn (Zea mays L.) 1,300-1,680 93 22
Cercospora zeae-maydis Corn 1,260 31 ± 8 144
Colletotrichum spp. Sorghum 2,000 40 5
Colletotrichum spp. Apple 3,554 40 29
Alternaria mali Apple 3,360 15 60
Alternaria spp. and Pear 3,200 63 ± 30 155
Stemphylium spp.
Colletotrichum acutatum Strawberry 1,600 21 (with yield 106
increase)
Cercospora arachidicola Peanut 2,400 93 ± 1 50, 94, 205
Rhizoctonia solani Soybean (Glycine max L.) 1,600 57 ± 10 123
Ascochyta rabiei Chick-pea 1,600-1,700 20 ± 9 36, 42
Alternaria alternata Olive (Olea europea L.) 1,944 86 21
Alternaria solani Potato 1,600-2,400 36 ± 20 95, 177
Fusarium oxysporum f. sp. Tomato 2,520 54 64
lycopersici
Septoria lycopersici Tomato 1,600-2,000 40 ± 15 45
Alternaria solani Tomato 1,600-2,000 43 ± 20 10, 99
Colletotrichum coccodes Tomato 1,680-2,500 57 ± 21 45
Phomopsis viticola Vine 1,920-3,600 73 ± 20 147, 148
Gloeosporium ampelophagum Vine 2,400 51 ± 18 198
Rhizoctonia solani Rosemary (Rosmarinus officinalis L.) 1,800 71 ± 20 82
Botrytis cinerea Rose 1,600 35 142
Botrytis cinerea Geranium (Pelargonium zonale) 500 50 ± 10 141
Botrytis elliptica Iris (Iris spp.) 1,350 90 34
Colletotrichum gloeosporioides Anemone (Anemone spp.) 1,600 45 73
Colletotrichum gloeosporioides Euonymus (Euonymus fortunei) 1,400 42 169
Septoria cornicola Red osier dogwood (Cornus sericea L.) 1,440 82 ± 15 18
Colletotrichum acutatum Azalea (Azalea japonica L.) 1,440 95 ± 5 17
Basidiomycetes Puccinia allii Garlic (Allium sativum L.) 1,600 65 32, 102, 103, 161
Puccinia asparagi Asparagus 1,400 49 149
Puccinia triticina Wheat 700-2,800 81 ± 9 25, 96, 118
Puccinia striiformis Barley (Hordeum vulgare L.) 1,600 50 ± 3 24, 115
Puccinia sorghi Corn 1,680 24 72
Puccinia sorghi Sorghum 1,260-2,000 52 ± 27 5, 206
Tranzschelia discolor Peach 2,000 76 33, 38
Tranzschelia discolor Plum (Prunus domestica L.) 1,600 73 ± 18 125, 197
Uromyces viciae-fabae Pea (Pisum sativum L.) 1,000-1,500 58 ± 2 182, 183
Uromyces appendiculatus Bean (Phaseolus vulgaris L.) 1,600 60 2
Puccinia arachidis Peanut 2,000-2,400 49 ± 12 94, 165, 205
Uromyces viciae-fabae Faba bean (Vicia faba L.) 800-1,360 57 ± 26 87, 88, 214
Puccinia hemerocallis Daylily (Hemerocallis spp.) 1,440 95 30
Puccinia horiana Chrysanthemum 1,400-1,600 45 ± 15 44, 212
(Chrysanthemum spp.)
Uredo spp. Daisy (Dendranthema frutescens) 1,600 85 ± 15 132
Puccinia pelargonii-zonalis Geranium 564 95 68
Uromyces caryophyllinus Carnation 2,000 50 ± 18 4
Bacteria Pseudomonas syringae Melon 1,575 59 110
Xanthomonas campestris pv. Cucumber 1,600 33 ± 4 184
cucurbitae
Xanthomonas vesicatoria Pepper (Capsicum annuum L.) 720-1,800 63 ± 1 16, 120

Plant Disease / September 2010 1079

cidal dip for certain plant parts used in vegetative propagation.
Mancozeb also plays an important role in the production of lower
acreage or so-called minor crops where the number of fungicides
available to growers is limited due to a relatively low total market
value and high registration costs creating a barrier to entry. In this
scenario, having an effective fungicide to help manage resistance
concerns is vital.
Usage and Effectiveness
Market share. Market analysis data show that approximately
$740 million worth of mancozeb-containing products were sold in
2007 (48). Around 85% of sales were split evenly between Europe
and the Asia Pacific regions, with only around 4% in the North
American markets. Potatoes and vegetables were the two largest
market segments, accounting for approximately 29 and 28% of
sales, respectively. Grapevines (18%) and fruit and nut crops
(19%) were the two next largest segments. The most important
uses in the EU include, but are not limited to, control of early and
late blight of tomato and potato (Fig. 2), control of downy mildews
on grapevines and vegetable and salad crops, and control of scab
on pome fruit. Potato, tomato, vine, and apple represent over 90%
of the total sales of mancozeb in Europe. In North America, key
uses today are within the vegetable crops, with a particular focus on
tomatoes, onions, and cucurbits, and in Central and Latin America,
potatoes and bananas (Fig. 3) are significant markets for the product.
A more detailed analysis of mancozeb and competitor multi-site
fungicide use on potatoes, grapevines, and tomatoes in the key
Western European fungicide markets of France, Germany, Italy,
UK, Spain, and Portugal is presented (Tables 3 to 5). The data are
drawn from in-house analysis of pesticide usage statistics reported
into Agrobase from 2001 to 2007 and as such are estimates of rela-
tive use patterns rather than absolute figures. Looking at the per-
centage of treated super-developed area (high input intensively
farmed land in order to maximize possible yield), we see that man-
cozeb is clearly the leading multi-site in potato (Table 3), which is
almost exclusively driven by need to control Phytophthora in-
festans. On grapevines, use patterns tend to vary more among
countries. In France, which is the largest grapevine market in
Europe, mancozeb is used on around 20% of super-developed hec-
tares in contrast with folpet (40%) (Table 4). Italy has more of a
tradition of using copper in vine spray programs, and this material
is used on 42% of Italian super-developed hectares, which is
slightly more than mancozeb (39%). On tomato in Italy, copper is
used on twice as many hectares as mancozeb (57 versus 26%), and
on the same crop in Spain, chlorothalonil, mancozeb, and copper
show equal levels of use at 26, 26, and 21% of super-developed
areas, respectively (Table 5).

Table 3. Use patterns for multi-site fungicides on potato in France,

Germany, and the UK (% of super-developed area [SDA] treated)a
% of SDA ha treatedb
Active substance France Germany UK
Mancozeb 62 44 37
Metiram 0.6 1.7 0
Maneb 7 8.7 0
Chlorothalonil 3 0 1.7
Copper 1.3 0.3 0
Folpet 0.6 0 0
Propineb 1 0 0
a Source: Agrobase.
Fig. 2. Control of Phytophthora infestans in potato fungicide efficacy trial. Treated b SDA treated: France, 2,664,000 ha; Germany, 1,755,000 ha; and
strip plots were sprayed with eight applications of mancozeb (2 kg a.i./ha) at 7-day UK, 893,000 ha.
intervals and are separated by 1-m-wide untreated rows.

Fig. 3. Control of Mycosphaerella fijiensis in banana fungicide efficacy trial. A, Untreated plot showing typical symptomology. B, Treated plot (T5) was sprayed with eight
applications of mancozeb (1 kg a.i./ha) at 10-day intervals.

1080 Plant Disease / Vol. 94 No. 9

 Role of mancozeb in anti-resistance strategies. Fungicide re-
sistance is a serious and intensively studied issue in the manage-
ment of many key fungal diseases of most crops. It threatens the
commercial potential of products, particularly those having a sin-
gle-site mode of action. The history of resistance developing to
fungicides since the early 1970s is well documented (163). Major
classes of single-site inhibitors such as the benzimidazoles,
pyrimidines, carboxanilides, phenylamides, sterol biosynthesis
inhibitors, morpholines, and QoI inhibitors have all seen cases of
resistance developing in various fungal pathogens (63). In some
extreme cases, significant crop losses have resulted, and some
products have been lost as effective tools on certain crops.
The development of resistance in a fungal population is the in-
evitable response to the selection pressure of fungicide use. It may
be managed by applying resistance management strategies that aim
to reduce selection pressure. At the same time, a difficult balancing
between commercial needs and technical requirements is neces-
sary. On one hand, a company needs to sell products that have cost
many millions of dollars to develop; on the other hand, it is neces-
sary to reduce fungicide use to prolong the life and economic value
of the product. Mixtures of fungicides that combine a high resis-
tance risk with a low risk multi-site compound or another single-
site fungicide that is not cross-resistant to its mixing partner are a
common response to this problem. In addition, recommending
rotations of fungicides with different modes of action within a
spray program as well as placing a cap on the number of applica-
tions that can be made in a season with a particular product are all
tested strategies. Mancozeb’s role as a key tool within resistance
management strategies is firmly grounded on the intrinsically low
resistance risk of the molecule itself. Mancozeb’s activity at multi-
ple sites within the target fungus precludes the possible develop-
ment of monogenic target site resistance. Mutations within multi-
ple genes would need to occur within fungal isolates in a situation
analogous to polygenic resistance where an associated gradual
decline in efficacy would be seen to occur over time. There is no
empirical evidence for this having occurred with mancozeb in any
target pathogen. A more likely potential resistance mechanism
would be based on detoxification of the active fungicide. This
mechanism has been described for a number of different fungicides
in various pathogens including the multi-site fungicide captan in
Botrytis cinerea (12). The same authors reported cross-resistance
between the captan-resistant B. cinerea isolates and five other fun-
gicides: folpet, captafol, etem, chlorothalonil, and the EBDC
thiram. The authors suggest that the mechanism of resistance may
be due to over production of thiols which detoxify the fungicides.
Experimental data relating to the effectiveness of mixture and
rotation strategies with fungicides are limited (27). Growth-room
and plastic-tunnel studies showed that applications of mixtures of a
phenylamide fungicide with mancozeb or mancozeb plus cymox-
anil for the control of Phytophthora infestans decreased the build-
up of phenylamide resistance compared with phenylamide applied
alone (166,191). Specifically in greenhouse and field tests,
oxadixyl-mancozeb mixtures (and any other phenylamide in com-
bination with contact fungicides) provided strong synergistic inter-
actions (71). In 1980, the dramatic occurrence of practical resis-
tance problems related to the use of phenylamides in different parts
of the world on various crops played an important role in the for-
mation of FRAC and, subsequently, of the FRAC Phenylamides
Working Group, which produced guidelines for resistance avoid-
ance. It was clearly observed that use of metalaxyl alone for the
control of potato late blight led to resistance, which, on the other
hand, did not occur in those countries where only formulated mix-
tures with mancozeb were applied (190). Although FRAC recom-
mendations could not totally prevent the appearance and spread of
resistant variants of Phytophthora infestans, there is evidence from
field experiments that phenylamide-mancozeb mixtures continued
to perform better than mancozeb alone (190), even in re-entry
situations where a phenylamide alone was originally used and then
withdrawn (49).
In the past, the quick adaptation of many pathogens to benzimi-
dazoles was often recorded. An example of the successful early use
of a mixture strategy was the application of benzimidazoles in the
United States to control Cercospora leaf-spots of peanut. Resis-
tance soon appeared in the southeastern states, where there was
sole use of benomyl, whereas in Texas, where benzimidazole–man-
cozeb mixtures were used from the very beginning, no resistance
developed over many years (185).
In the case of QoI fungicides, selection for resistance in Plasmo-
para viticola was delayed by a mixture with folpet, fosetyl-alumi-
num, or mancozeb (67). It was also shown that rate of selection for
resistance to azoxystrobin in P. viticola is delayed when the prod-
uct is mixed with mancozeb (178).
Table 5. Use patterns for multi-site fungicides on tomato in Italy
and Spain (% of super-developed area [SDA] treated)a
% of SDA ha treatedb
Active substance Italy Spain
Mancozeb 26 26
Metiram 0.5 9.8
Maneb 0 3.2
Chlorothalonil 5.2 26
Copper 57 21
Folpet 0.5 0
Propineb 0 1.6
a Source: Agrobase.
b SDA treated: Italy, 439,000 ha; and Spain 61,000 ha.

Table 4. Use patterns for multi-site fungicides on grapevine in France, Germany, Italy, Spain, and Portugal (% of super-developed area [SDA]
treated)a
% of SDA ha treatedb
Active substance France Germany Italy Spain Portugal
Mancozeb 20 8.4 39 23 29
Metiram 11 26 3.5 0.1 2.2
Maneb 1.4 0 0 0 0
Chlorothalonil 0.1 0 0 0 0
Copper 20 34 42 49 16
Folpet 42 8.8 4 24 30
Dithianon 0 3.2 0 0 0
Propineb 0.1 0.3 0.1 0 24
Captan 0 0 0 2 0
Tolyfluanid 0 3.9 0.5 0 0
a Source: Agrobase.
b SDA treated: France, 13,937,000 ha; Germany, 1,076,000 ha; Italy, 5,499,000 ha; Spain, 1,205,000 ha; and Portugal, 660,000 ha.

Plant Disease / September 2010 1081

 In order to avoid risks related to resistance development, manu-
facturers’ recommended doses of fungicides must be maintained,
although relationships of fungicide dose to risks of resistance are
not yet fully understood. Lowering the dose of an at-risk fungicide
can delay the build-up of major-gene resistance, but on the other
hand, it may enhance resistance development relevant to multi-step
resistance (27). Experimental data reflect uncertainty about this
kind of behavior. For instance, when a benomyl–mancozeb mixture
was applied to control apple scab, build-up of benomyl resistance
was delayed by reducing the benomyl concentration and increasing
the mancozeb concentration (108).
The role of mancozeb for disease control in minor crops in
Europe. The protection of minor crops is becoming an increas-
ingly important issue in many countries. A crop is defined as “mi-
nor” in terms of cultivated surface area (56) or in terms of its rela-
tive contribution to human diet. Several critical points are related to
disease control in minor crop production, including a limited num-
ber of registered fungicides (70,83), short crop cycles, emergence
of resistance or lower sensitivity toward certain compounds, and
emergence of new diseases for which no effective control measure
exists. Most minor crops, which may be of local importance to the
economies of certain countries or regions, are simply not large
enough to produce an attractive commercial return after factoring
in the cost of obtaining a registration (81). The vegetable market is
a good example of this conundrum in that it is highly segmented in
terms of crops cultivated and target pathogens. The Mediterranean
region is characterized by a highly diverse agriculture; and Italy,
which cultivates a wide range of minor crops, is an excellent model
country with which to illustrate the main issues in this area. A
number of minor crops cultivated in Italy encounter major prob-
lems with respect to available disease-control solutions. These
crops are cultivated on significant areas locally although still con-
sidered minor on a national scale. Examples include: vegetables
such as cabbage, parsley, French bean, and arugula; species culti-
vated for seed production (equivalent to around 10,000 ha); soft
fruit such as raspberry, currants, and gooseberry (cultivated on 448
ha) (85); minor fruit crops such as apricot, tangerine, cherry, plum,
and also flower crops.
Lacking a range of fungicides with differing modes of action
means that managing potential resistance development in certain
diseases on minor crops can be particularly difficult for growers
(19). This is where a tool such as mancozeb becomes particularly
valuable due to its wide breadth of crop registrations and utility in
resistance risk management. In the EU, France currently has a total
of 42 crops on the mancozeb label (Dithane NT), several of which
are considered minor crops under the definition of this grouping in
France. As such, the product is seen as a key tool for French minor
crop growers.
In Italy, mancozeb-based fungicides are currently registered on
cereals, tomato, potato, tobacco, poplar, grapevine, apple, pear, carna-
tion, and rose. The use of different mancozeb-based fungicides for
vegetable seed treatment in Italy also provides control of many emerg-
ing seed-transmitted pathogens (69,199), although this use pattern
will probably be lost in the future following re-registration in Italy.
As part of the current Annex III re-registration process for man-
cozeb in Italy, the label will be expanded to include a wide range
of additional crops, of which 44 might be considered minor.
The availability of fungicides for the protection of minor crops
is becoming a key issue in Europe due to the ongoing loss of active
ingredients from the market as a result of the EU Commissions re-
registration process (91/414). Proposed revisions to 91/414, which
are currently undergoing debate at the European Commission,
could potentially reduce drastically the number of registrations in
future years. In Italy, significant yield and economic losses are
foreseen for many niche crops if appropriate countermeasures are
not taken. In other EU countries, countermeasures have been taken.
These include the approval of new pesticide uses (2,222 total in
Germany from 2000 to 2006, of which 27% were for minor uses)
(90) or use of so-called specific off-label approvals as practiced in
countries such as the UK and Denmark (28,35).
1082 Plant Disease / Vol. 94 No. 9
Current Limitations and Critical Issues
Implications of use rate. Mancozeb is a typical multi-site pro-
tectant-only fungicide. For this reason, use rates and frequency of
application need to be relatively high in order to counteract the
effects of weathering and plant growth, which can rapidly diminish
the protection afforded by the product. It must also be present on
the leaf prior to the arrival of fungal spores if it is to be effective,
and hence it is not as flexible as curative or eradicant chemistries.
Traditionally, mancozeb and other multi-site protectant fungicides
have been used in a classic prophylactic approach to disease con-
trol where applications are made on a routine calendar spray sched-
ule. This approach has proved to be very effective from both a cost
and disease control perspective. However, it does not fit well with
the basic tenets of Integrated Pest Management (IPM), where pesti-
cides inputs should not be used unless absolutely necessary.
Mancozeb has recently (2005) been granted Annex I re-registra-
tion in Europe under the 91/414 directive at a use rate of 1.6 kg
a.i./ha across a wide range of crops. Although this represents a
reduction in compound applied from previous label rates in most
crops, it is still 5 to 10 times higher than that of more modern se-
lective systemic chemistries such as triazoles and strobilurins when
used to control the same pathogens. The holy grail for agrochemi-
cal industry fungicide discovery programs can probably be defined
as a product with low use rate, multi-site mode of action (i.e., low
resistance risk), systemic properties, good plant selectivity, and an
excellent regulatory profile.
Safety to beneficials. Mancozeb has a generally favorable
ecotoxicological profile (126), although its negative impact on
phytoseiid predatory mites and in particular Typhlodromus pyri has
been well reported (20,117,173). This observation has its origins in
studies undertaken using historical use patterns where mancozeb
was used for season-long disease control in vines at rates as high as
2.8 kg a.i./ha applied 6 to 10 times per season. In modern agro-
nomic cropping systems in orchards and vineyards, mancozeb is
more typically used in tank mixture or co-formulated with specific
systemic chemistries. The combination of a newly registered EU
use rate of 1.6 kg a.i./ha and a reduction in permitted applications
to no more than four per season has led to the development of man-
cozeb spray programs in vines and pome crops with a reduced
impact on predatory mites. Field studies conducted over 2 years in
five different vine and apple growing regions in Europe indicated
that two to four applications of mancozeb at 1.6 kg a.i./ha caused
minimal impact on naturally occurring populations of predatory
mites and other relevant entomofauna (127,128).
Regulatory pressures: past, present, and future. The future
health of the global economy and the public’s perception of the
agrochemical industry are two key issues for the sustainability of
the pesticide market as we move forward in the twenty-first cen-
tury. Governments worldwide are pursuing reductions in pesticide
use via legislation tied directly to agricultural policy along with
moves toward more sustainable agricultural production systems.
Being forthright in the pursuit of sustainability is key for the pesti-
cide industry if it is to continue to do business in the twenty-first
century. As a well-known and globally significant group of crop
protection products, the EBDCs are frequently selected as partici-
pants in so-called market basket surveys, which are routinely con-
ducted by the authorities in order to monitor for pesticide residues
and violation of minimum residue levels (MRLs) in the food chain.
Since the 1970s, EBDCs including mancozeb have undergone
extensive regulatory review in many countries, primarily because
of their frequency of use and worldwide importance to agriculture.
Extensive research on mancozeb and its metabolite of primary
regulatory concern, i.e., ethylenethiourea (ETU), has been con-
ducted and published (78). These reviews cover the mode of ac-
tion, toxicity, and metabolism in animals, plants, and the environ-
ment. International monographs and compilations of studies on
EBDCs and ETU are available, including significant regulatory
reviews by the World Health Organization (WHO) and the Food
and Agriculture Organization (FAO) (58,207). The U.S. Environ-
mental Protection Agency (EPA) conducted an extensive special
review of EBDCs including mancozeb from 1987 to 1992, and in
2005, the EPA granted re-registration of mancozeb in the United
States. Mancozeb was also granted Annex I re-registration under
the 91/414 directive in the EU in 2005. The common theme run-
ning through these extensive reviews by key government and inter-
national regulatory agencies is that rigorous scientific examination
of the available data continues to support the view that mancozeb,
when used according to label directions, is acceptable for use in
modern agricultural production systems with respect to its impact
on the consumer, user, and the environment. No doubt the regula-
tory introspection of a well-used and globally important product
such as mancozeb will continue into the foreseeable future in what
is becoming an ever changing and more demanding regulatory
landscape for pesticides.
Perspectives
For more than 46 years, mancozeb has been an invaluable tool to
growers around the world faced with the challenge of controlling
fungal pests in their crops. When selecting agrochemical inputs for
use on their crops, growers are looking for products that are effica-
cious, safe to the crop and environment, and above all, cost-effec-
tive. Mancozeb fits well in all these categories, and its continued
popularity as it approaches half a century on the market is testa-
ment to the value it brings as a useful tool within many modern
agronomic production systems. At the time this article was written,
the agrochemical industry has yet to develop another product with
the combination of properties (i.e., efficacy, broad-spectrum, crop
safety, low resistance risk, and low cost) that make mancozeb so
successful. In an ever more demanding and uncertain regulatory
landscape, pesticides such as mancozeb will continue to face chal-
lenges with respect to re-registration in the years to come. With the
world’s population predicted to grow by around 50% to 9 billion
by 2050, it is clear that we are faced with the major challenge of
significantly increasing yields from a finite area of productive ar-
able land (187). Control of economically important plant patho-
gens will continue to be key if this target is to be met, and farmers
in both the industrialized and developing world will still need and
desire access to cost-effective efficacious tools such as mancozeb.
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19.
 Maria Lodovica Federico Tinivella Angelo Garibaldi
Gullino
Dr. Gullino has spent her career at the University of Torino,
where she is professor in Biological and Integrated Plant
Disease Management, School of Biotechnology, Director of
the Centre of Competence AGROINNOVA, and Vice-Rector
for International Affairs. In the 1980s, she spent various
research periods in universities in the Netherlands (Wagen-
ingen University) and in the United States (Maryland, Cornell,
and Penn State). She was vice-president of the International
Society for Plant Pathology (ISPP) from 2003 to 2008 and is
now president from 2008 to 2013. She is also past-president
of the Italian Society for Crop Protection (A.I.P.P.) and of the
Italian Association of the Agricultural Scientific Societies
(AISSA). Her research interests focus on plant disease
management, biological and integrated control of diseases,
crop biosecurity, effect of climate change on plant diseases,
and sustainable agriculture. Lodovica Gullino has always
been interested in international activities in the fields of
research, teaching, and knowledge and technology transfer.
Since 1998, she has been in charge of the international
affairs of the University of Torino, and in 2002, she and
Angelo Garibaldi started AGROINNOVA, a Centre of Com-
petence in the agro-environmental and agro-food sector,
which rapidly gained national and international recognition.
Dr. Tinivella is an agronomist and extension plant
pathologist. He received his M.S. in agricultural sciences from
the University of Torino (Italy) in 2001 and his Ph.D. in plant
pathology from the same university in 2006. He spent
different periods of study abroad in Sweden, Denmark, and
the United States. His field of research was treatment of
vegetable seeds as an alternative to the use of chemicals and
disease control of key vegetable crops of the Mediterranean
area. He worked in the crop biosecurity sector in the frame of
collaboration projects between the University of Torino,
Kansas State University, and the Great Plains Diagnostic
Network (U.S.). He served for 4 years as coordinator of the
Italian review of crop protection “Informatore Fitopatologico –
La Difesa delle piante” edited by Il Sole 24 Ore Edagricole
s.r.l. He now works as a consultant of farms operating in the
sector of ornamentals and vegetable crops.
Dr. Garibaldi has spent his career at the University of
Torino, where he is professor of Plant Disease Management,
president of the Centre of Competence AGROINNOVA, mem-
ber of the Board of the University, and chairman of Com-
mission Spin-off of the same University. In the 1960s and
1970s, he spent research periods in the United States, Israel,
France, and Netherlands. He supervised several students in
the preparation of their Masters and Ph.D. theses in Italy and
abroad. His research interests focus on plant disease man-
agement, biological control of diseases, and diseases of
ornamental and vegetable crops. He has co-authored several
books and published over 800 scientific articles and reviews
in Italian and international journals. In 2002, together with
Maria Lodovica Gullino, he started AGROINNOVA, a Centre
of Competence in the agro-environmental and agro-food
sector, which rapidly gained national and international
recognition. In 2008, he launched a new Italian journal of crop
protection (Protezione delle Culture). He organized courses at
the national and international level for training technicians
Gregory M. Leonardo Bacci Brian Russell
Kemmitt Sheppard
and researchers working in the fields of plant pathology and of
plant disease management.
Dr. Kemmitt is the current Global R&D leader for fungicide
development at Dow AgroSciences. He received a B.Sc. in
applied plant sciences from the University of London in 1989
and a Ph.D. in plant pathology from the University of Wales in
1993. He joined DowElanco in the UK in 1992 as a
postdoctoral research fellow working in early-stage discovery
fungicide screening. From 1994 to 2001 he was located in
Indianapolis, IN, USA, where he worked in a variety of roles
including early- to late-stage glasshouse fungicide screening,
field trials scientist, and management of the Dow Agro-
Sciences global fungicide field trials characterization program.
In 2001, he moved back to the UK to take on the role of
technology transfer and technical support for the Dow
AgroSciences fungicide portfolio. He is a member of the
Fungicide Resistance Action Committee (FRAC) steering
team. His research interests are in the area of chemical
control of plant diseases.
Dr. Bacci spent his career at Dow AgroSciences, where he
is Biology Team Leader and Technology Transfer Educator for
Top Fruits and Grape. He joined the company in 1980 and the
focus of his career has been in field research and
development, starting with pyrimidines and dinitroanilines. As
project leader for Top Fruits, Grape and Vegetables, during the
period from 1990 to 1995, he provided technical inputs for
quinolines and quinazolines, with an innovative co-
development approach that involved major IPM and Food
Chain players in South Europe. His R&D activity promoted
scientific relationships with university, plant protection asso-
ciations, and Italy Centre of Competence (AGROINNOVA) for
Plant Disease Management, Integrated Control of Diseases,
Agro-Environmental and Agro-Food Security. His depth of
technical knowledge was influential during the period from
1995 to 2000 for a rapid characterization of triazolopyri-
midines and for an innovative experimental project of sus-
tainable use, of soil Fumigant 1,3d in Southern Italy. As tech-
nical expert, from 2000 to 2005, after the acquisition of Rohm
& Haas, he merged, within the Fungicide Global Business Unit
of Dow AgroSciences, the culture of triazoles, dinitrophenols,
and oomycete fungicides mancozeb and zoxamide in Mediter-
ranean crops, managing the impact on Food Chain and
Processor Tomato Industries.
Dr. Sheppard spent his entire career at Dow AgroSciences,
working in both the herbicide and fungicide disciplines in
numerous roles at various locations. While living in Canada,
England, and France, he developed herbicides for use in the
cereals, canola, and IVM (Industrial Vegetation Management)
markets. While living in various states in the United States, he
developed herbicides for use in the corn, soybean, range and
pasture, and IVM markets, both within the United States and
globally. He spent the last 9 years of his career developing
fungicides in numerous markets around the world, during
which time he was the global technical manager for
mancozeb. After 34 years of service, he retired December 31,
2009 with his last role being R&D manager of the global
fungicide business.
Plant Disease / September 2010 1087