HistoryEdit

Prior to the widespread use of herbicides, cultural controls, such as

altering soil pH, salinity, or fertility levels, were used to control weeds.
[5] Mechanical control (including tillage) was also (and still is) used to control
weeds.
First herbicidesEdit

2,4-D, the first chemical herbicide, was discovered during the Second World War.

Although research into herbicides began in the early 20th century, the first
major breakthrough was the result of research conducted in both the United
Kingdom and the United States during the Second World War into the
potential use of herbicides in war.[6] The first modern herbicide, 2,4-D, was
first discovered and synthesized by W. G. Templeman at Imperial Chemical
Industries. In 1940, he showed that "Growth substances applied
appropriately would kill certain broad-leaved weeds in cereals without
harming the crops." By 1941, his team succeeded in synthesizing the
chemical. In the same year, R. Pokorny in the US achieved this as well. [7]
Independently, a team under Juda Hirsch Quastel, working at
the Rothamsted Experimental Station made the same discovery. Quastel was
tasked by the Agricultural Research Council (ARC) to discover methods for
improving crop yield. By analyzing soil as a dynamic system, rather than an
inert substance, he was able to apply techniques such as perfusion. Quastel
was able to quantify the influence of various plant hormones, inhibitors, and
other chemicals on the activity of microorganisms in the soil and assess their
direct impact on plant growth. While the full work of the unit remained
secret, certain discoveries were developed for commercial use after the war,
including the 2,4-D compound.[8]
When 2,4-D was commercially released in 1946, it triggered a worldwide
revolution in agricultural output and became the first successful selective
herbicide. It allowed for greatly enhanced weed control
in wheat, maize (corn), rice, and similar cereal grass crops, because it
kills dicots (broadleaf plants), but not most monocots (grasses). The low cost
of 2,4-D has led to continued usage today, and it remains one of the most
commonly used herbicides in the world. Like other acid herbicides, current
formulations use either an amine salt (often trimethylamine) or one of
many esters of the parent compound. These are easier to handle than the
acid.
Further discoveriesEdit
The triazine family of herbicides, which includes atrazine, was introduced in
the 1950s; they have the current distinction of being the herbicide family of
greatest concern regarding groundwater contamination. Atrazine does not
break down readily (within a few weeks) after being applied to soils of above-
neutral pH. Under alkaline soil conditions, atrazine may be carried into the
soil profile as far as the water table by soil water following rainfall causing
the aforementioned contamination. Atrazine is thus said to have "carryover",
a generally undesirable property for herbicides.
Glyphosate (Roundup) was introduced in 1974 for nonselective weed control.
Following the development of glyphosate-resistant crop plants, it is now used
very extensively for selective weed control in growing crops. The pairing of
the herbicide with the resistant seed contributed to the consolidation of the
seed and chemistry industry in the late 1990s.
Many modern herbicides used in agriculture and gardening are specifically
formulated to decompose within a short period after application. This is
desirable, as it allows crops and plants to be planted afterward, which could
otherwise be affected by the herbicide. However, herbicides with low residual
activity (i.e., that decompose quickly) often do not provide season-long weed
control and do not ensure that weed roots are killed beneath construction
and paving (and cannot emerge destructively in years to come), therefore
there remains a role for weed killer with high levels of persistence in the soil.
TerminologyEdit

Herbicides are classified/grouped in various ways; for example, according to

the activity, the timing of application, method of application, mechanism of
action, and chemical family. This gives rise to a considerable level of
terminology related to herbicides and their use.

Intended outcomeEdit
 Control is the destruction of unwanted weeds or the damage of them to the
point where they are no longer competitive with the crop.
 Suppression is incomplete control and still provides some economic benefits,
such as reduced competition with the crop.
 Crop safety, for selective herbicides, is the relative absence of damage or
stress to the crop. Most selective herbicides cause some visible stress to crop
plants.
 Defoliant, similar to herbicides, but designed to remove foliage (leaves)
rather than kill the plant.

Selectivity (all plants or specific plants)Edit

 The basis of selectivity is based on physical or biological factors. Some
biological factors include morphology, physiology, metabolism, and
biochemical factors.
 There are some climatic factors affecting absorption including humidity, light,
precipitation, and temperature. Foliar-applied herbicides will enter the leaf
more readily at high humidity by lengthening the drying time of the spray
droplet and increasing cuticle hydration. Light of high intensity may break
down some herbicides and cause the leaf cuticle to thicken, which reduces
absorption. Precipitation may wash away or remove some foliar-applied
herbicides but it will increase root absorption of soil-applied herbicides.
Drought-stressed plants are less likely to translocate herbicides. As
temperature increases, herbicides' performance may decrease. Absorption
and translocation may be reduced in very cold weather.

 Selective herbicides control or suppress certain plants without affecting the

growth of other plant species. Selectivity may be due to translocation,
differential absorption, or physical (morphological), or physiological
differences between plant species. Surfactants alter the physical properties of
the spray solution and the overall phytotoxicity of the herbicide, increasing
translocation. 2,4-D, mecoprop, and dicamba control many broadleaf weeds
but remain ineffective against turf grasses. [9]
  Non-selective herbicides are not specific in acting against certain plant
species and control all plant material with which they come into contact. They
are used to clear industrial sites, waste grounds, railways, and railway
embankments. Paraquat, glufosinate, and glyphosate are non-selective
herbicides.[9]

Timing of applicationEdit
 Preplant: Preplant herbicides are nonselective herbicides applied to the soil
before planting. Some preplant herbicides may be mechanically incorporated
into the soil. The objective for incorporation is to prevent dissipation
through photodecomposition and/or volatility. The herbicides kill weeds as
they grow through the herbicide-treated zone. Volatile herbicides have to be
incorporated into the soil before planting the pasture. Agricultural crops
grown in soil treated with a preplant herbicide include tomatoes, corn,
soybeans, and strawberries. Soil fumigants like metam-
sodium and dazomet are in use as preplant herbicides. [9]
 Preemergence: Preemergence herbicides are applied before the weed
seedlings emerge through the soil surface. Herbicides do not prevent weeds
from germinating but they kill weeds as they grow through the herbicide-
treated zone by affecting the cell division in the emerging
seedling. Dithiopyr and pendimethalin are preemergence herbicides. Weeds
that have already emerged before application or activation are not affected
by pre-herbicides as their primary growing point escapes the treatment. [9]
 Postemergence: These herbicides are applied after weed seedlings have
emerged through the soil surface. They can be foliar or root absorbed,
selective or nonselective, and contact or systemic. Application of these
herbicides is avoided during rain since being washed off the soil makes it
ineffective. 2,4-D is a selective, systemic, foliar-absorbed postemergence
herbicide.[9]

Method of applicationEdit
 Soil applied: Herbicides applied to the soil are usually taken up by the root or
shoot of the emerging seedlings and are used as preplant or preemergence
treatment. Several factors influence the effectiveness of soil-applied
herbicides. Weeds absorb herbicides by both passive and active mechanisms.
Herbicide adsorption to soil colloids or organic matter often reduces the
amount available for weed absorption. Positioning of the herbicide in the
correct layer of soil is very important, which can be achieved mechanically
and by rainfall. Herbicides on the soil surface are subjected to several
processes that reduce their availability. Volatility and photolysis are two
common processes that reduce the availability of herbicides. Many soil-
applied herbicides are absorbed through plant shoots while they are still
underground leading to their death or injury. EPTC and trifluralin are soil-
applied herbicides.[9]
  Foliar applied: These are applied to a portion of the plant above the ground
and are absorbed by exposed tissues. These are generally postemergence
herbicides and can either be translocated (systemic) throughout the plant or
remain at a specific site (contact). External barriers of plants like cuticles,
waxes, cell walls etc. affect herbicide absorption and action. Glyphosate, 2,4-
D, and dicamba are foliar-applied herbicides. [9]

PersistenceEdit
 Residual activity: An herbicide is described as having low residual activity if it
is neutralized within a short time of application (within a few weeks or
months) – typically this is due to rainfall, or reactions in the soil. A herbicide
described as having high residual activity will remain potent for the long term
in the soil. For some compounds, the residual activity can leave the ground
almost permanently barren.

Use and applicationEdit

Herbicides being sprayed from the spray arms of a tractor in North Dakota.

Most herbicides are applied as water-based sprays using ground equipment.

Ground equipment varies in design, but large areas can be sprayed using
self-propelled sprayers equipped with long booms, of 60 to 120 feet (18 to
37 m) with spray nozzles spaced every 20–30 inches (510–760 mm) apart.
Towed, handheld, and even horse-drawn sprayers are also used. On large
areas, herbicides may also at times be applied aerially using helicopters or
airplanes, or through irrigation systems (known as chemigation).
A further method of herbicide application developed around 2010, involves
ridding the soil of its active weed seed bank rather than just killing the weed.
This can successfully treat annual plants but not perennials. Researchers at
the Agricultural Research Service found that the application of herbicides to
fields late in the weeds' growing season greatly reduces
their seed production, and therefore fewer weeds will return the following
season. Because most weeds are annuals, their seeds will only survive in soil
for a year or two, so this method will be able to destroy such weeds after a
few years of herbicide application.[24]
Weed-wiping may also be used, where a wick wetted with herbicide is
suspended from a boom and dragged or rolled across the tops of the taller
weed plants. This allows treatment of taller grassland weeds by direct
contact without affecting related but desirable shorter plants in
the grassland sward beneath. The method has the benefit of avoiding spray
drift. In Wales, a scheme offering free weed-wiper hire was launched in 2015
in an effort to reduce the levels of MCPA in water courses.[25]
There is little difference in forestry in the early growth stages, when the
height similarities between growing trees and growing annual crops yields a
similar problem with weed competition. Unlike with annuals however,
application is mostly unnecessary thereafter and is thus mostly used to
decrease the delay between productive economic cycles of lumber crops. [26]

Misuse and misapplicationEdit

Herbicide volatilisation or spray drift may result in herbicide affecting
neighboring fields or plants, particularly in windy conditions. Sometimes, the
wrong field or plants may be sprayed due to error.
Although herbicidal warfare uses chemical substances, its main purpose is to
disrupt agricultural food production and/or to destroy plants which provide cover or
concealment to the enemy. During the Malayan Emergency (1948–1960), the British
military deployed herbicides and defoliants in the Malaysian countryside (including
crop fields) in order to deprive Malayan National Liberation Army (MNLA) insurgents
of cover, potential sources of food and to flush them out of the jungle. Deployment
of herbicides and defoliants served the dual purpose of thinning jungle trails to
prevent ambushes and destroying crop fields in regions where the MNLA was active
to deprive them of potential sources of food. Herbicides and defoliants were also
sprayed from Royal Air Force (RAF) aircraft.[27] The use of herbicides as a chemical
weapon by the U.S. military during the Vietnam War has left tangible, long-
term impacts upon the Vietnamese people and U.S soldiers that handled the
chemicals.[28][29] More than 20% of South Vietnam's forests, and 3.2% of its
cultivated land were sprayed at least once between during the war. [30] The
government of Vietnam says that up to four million people in Vietnam were exposed
to the defoliant, and as many as three million people have suffered illness because
of Agent Orange,[31] while the Red Cross of Vietnam estimates that up to one million
people were disabled or have health problems as a result of exposure to Agent
Orange.[32] The United States government has described these figures as
unreliable.[33]
Health and environmental effectsEdit
See also: Environmental effects of pesticides and Health effects of pesticides

Herbicides have widely variable toxicity in addition to acute toxicity arising

from ingestion of a significant quantity rapidly, and chronic toxicity arising
from environmental and occupational exposure over long periods. Much
public suspicion of herbicides revolves around a confusion between valid
statements of acute toxicity as opposed to equally valid statements of lack
of chronic toxicity at the recommended levels of usage. For instance, while
glyphosate formulations with tallowamine adjuvants are acutely toxic, their
use was found to be uncorrelated with any health issues like cancer in a
massive US Department of Health study on 90,000 members of farmer
families for over a period of 23 years.[34] That is, the study shows lack of
chronic toxicity, but cannot question the herbicide's acute toxicity.
Some herbicides cause a range of health effects ranging from skin rashes to
death. The pathway of attack can arise from intentional or unintentional
direct consumption, improper application resulting in the herbicide coming
into direct contact with people or wildlife, inhalation of aerial sprays, or food
consumption prior to the labelled preharvest interval. Under some
conditions, certain herbicides can be transported via leaching or surface
runoff to contaminate groundwater or distant surface water sources.
Generally, the conditions that promote herbicide transport include intense
storm events (particularly shortly after application) and soils with limited
capacity to adsorb or retain the herbicides. Herbicide properties that
increase likelihood of transport include persistence (resistance to
degradation) and high water solubility.[35]
Phenoxy herbicides are often contaminated with dioxins such as TCDD;[36]
[
citation needed] research has suggested such contamination results in a small
rise in cancer risk after occupational exposure to these herbicides.
[37] Triazine exposure has been implicated in a likely relationship to
increased risk of breast cancer, although a causal relationship remains
unclear.[38]

Herbicide manufacturers have at times made false or misleading claims

about the safety of their products. Chemical manufacturer Monsanto
Company agreed to change its advertising after pressure from New York
attorney general Dennis Vacco; Vacco complained about misleading claims
that its spray-on glyphosate-based herbicides, including Roundup, were safer
than table salt and "practically non-toxic" to mammals, birds, and fish
(though proof that this was ever said is hard to find). [39] Roundup is toxic and
has resulted in death after being ingested in quantities ranging from 85 to
200 ml, although it has also been ingested in quantities as large as 500 ml
with only mild or moderate symptoms.[40] The manufacturer of Tordon
101 (Dow AgroSciences, owned by the Dow Chemical Company) has claimed
Tordon 101 has no effects on animals and insects, [41] in spite of evidence of
strong carcinogenic activity of the active ingredient, [42] picloram, in studies
on rats.[43]
The risk of Parkinson's disease has been shown to increase with occupational
exposure to herbicides and pesticides.[44] The herbicide paraquat is
suspected to be one such factor.[45]
The Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA) requires all
pesticides sold or distributed in the United States (including imported
pesticides) to be registered by the Environmental Protection Agency (EPA)
and the registration must be reviewed at least every 15 years. [46] However,
because of the large number of herbicides in use, concern regarding health
effects is significant. Herbicides often contain other ingredients (such as
emulsifiers) to enhance effectiveness, stability, or other properties. For
herbicides used in food production, inactive ingredients must have
tolerances or tolerance exemptions in the Code of Federal Regulations (CFR),
40 CFR part 180 (unless it is demonstrated that no residues are found in
food).[46]
Ecological effectsEdit
Commercial herbicide use generally has negative impacts on bird
populations, although the impacts are highly variable and often require field
studies to predict accurately. Laboratory studies have at times
overestimated negative impacts on birds due to toxicity, predicting serious
problems that were not observed in the field.[47] Most observed effects are
due not to toxicity, but to habitat changes and the decreases in abundance
of species on which birds rely for food or shelter. Herbicide use in silviculture,
used to favor certain types of growth following clearcutting, can cause
significant drops in bird populations. Even when herbicides which have low
toxicity to birds are used, they decrease the abundance of many types of
vegetation on which the birds rely.[26] Herbicide use in agriculture in the UK
has been linked to a decline in seed-eating bird species which rely on the
weeds killed by the herbicides.[48] Heavy use of herbicides
in neotropical agricultural areas has been one of many factors implicated in
limiting the usefulness of such agricultural land for wintering migratory birds.
[49]

Frog populations may be affected negatively by the use of herbicides as well.

While some studies have shown that atrazine may be a teratogen, causing
demasculinization in male frogs,[50] the EPA and its independent Scientific
Advisory Panel (SAP) examined all available studies on this topic and
concluded that "atrazine does not adversely affect amphibian gonadal
development based on a review of laboratory and field studies." [51]
Scientific uncertainty of full extent of herbicide effectsEdit
The health and environmental effects of many herbicides is unknown, and
even the scientific community often disagrees on the risk. For example, a
1995 panel of 13 scientists reviewing studies on the carcinogenicity of 2,4-
D had divided opinions on the likelihood 2,4-D causes cancer in humans.
[52] As of 1992, studies on phenoxy herbicides were too few to accurately
assess the risk of many types of cancer from these herbicides, even though
evidence was stronger that exposure to these herbicides is associated with
increased risk of soft tissue sarcoma and non-Hodgkin lymphoma.
[53] Furthermore, there is some suggestion that herbicides, as atrazine,
[54] can play a role in sex reversal of certain organisms that
experience temperature-dependent sex determination, which could
theoretically alter sex ratios.[55]

ResistanceEdit
One major drawback to the use of herbicides for weed control is the ability of
plants to evolve herbicide resistance, causing herbicides to no longer be
effective against target plants. Out of 31 known herbicide modes of action,
weeds have evolved resistance to 21. 268 plant species are known to have
evolved herbicide resistance at least once. [56] Herbicide resistance was first
observed in 1957, and since has evolved repeatedly in weed species from 30
families across the globe.[57] Weed resistance to herbicides has become a
major concern in crop production worldwide. [22] Resistance to herbicides is
often attributed to continuous applications of herbicides with the same sites
of action. Because of this, rotational programs of herbicide application,
where herbicides with multiple modes of action are used, have been widely
promoted. [23] In particular, glyphosate resistance evolved rapidly in part
because when glyphosate use first began, it was continuously and heavily
relied upon for weed control.[58] This caused incredibly strong selective
pressure upon weeds, encouraging mutations conferring glyphosate
resistance to persist and spread.[59]
However, in 2015, an expansive study showed an increase in herbicide
resistance as a result of rotation, and instead recommended mixing multiple
herbicides for simultaneous application. As of 2023, the effectiveness of
combining herbicides is also questioned, particularly in light of the rise of
non-target site resistance.[60][61][62]
Plants developed resistance to atrazine and to ALS-inhibitors relatively early,
but more recently,glyphosate resistance has dramatically risen. Marestail is
one weed that has developed glyphosate resistance. [63] Glyphosate-resistant
weeds are present in the vast majority of soybean, cotton and corn farms in
some U.S. states. Weeds that can resist multiple other herbicides are
spreading. Few new herbicides are near commercialization, and none with a
molecular mode of action for which there is no resistance. Because most
herbicides could not kill all weeds, farmers rotate crops and herbicides to
stop the development of resistant weeds.
A 2008–2009 survey of 144 populations of waterhemp in 41 Missouri
counties revealed glyphosate resistance in 69%. Weeds from some 500 sites
throughout Iowa in 2011 and 2012 revealed glyphosate resistance in
approximately 64% of waterhemp samples. As of 2023, 58 weed species
have developed glyphosate resistance.[64] Weeds resistant to multiple
herbicides with completely different biological action modes are on the rise.
In Missouri, 43% of waterhemp samples were resistant to two different
herbicides; 6% resisted three; and 0.5% resisted four. In Iowa 89% of
waterhemp samples resist two or more herbicides, 25% resist three, and
10% resist five.[58]
As of 2023, Palmer amaranth with resistance to six different herbicide modes
of action has emerged.[65] Annual bluegrass collected from a golf course in
the U.S. state of Tennessee was found in 2020 to be resistant to seven
herbicides at once.[66] Rigid ryegrass and annual bluegrass share the
distinction of the species with confirmed resistance to the largest number of
herbicide modes of action, both with confirmed resistance to 12 different
modes of action; however, this number references how many forms of
herbicide resistance are known to have emerged in the species at some
point, not how many have been found simultaneously in a single plant. [67][68]
In 2015, Monsanto released crop seed varieties resistant to both dicamba
and glyphosate, allowing for use of a greater variety of herbicides on fields
without harming the crops. By 2020, five years after the release of dicamba-
resistant seed, dicamba-resistant Palmer amaranth was found, meaning the
weed developed resistance twice as fast as the dicamba-resistant crops
could be developed.[69]
Resistance managementEdit
Worldwide experience has been that farmers tend to do little to prevent
herbicide resistance developing, and only take action when it is a problem on
their own farm or neighbor's. Careful observation is important so that any
reduction in herbicide efficacy can be detected. This may indicate evolving
resistance. It is vital that resistance is detected at an early stage as if it
becomes an acute, whole-farm problem, options are more limited and
greater expense is almost inevitable. Table 1 lists factors which enable the
risk of resistance to be assessed. An essential pre-requisite for confirmation
of resistance is a good diagnostic test. Ideally this should be rapid, accurate,
cheap and accessible. Many diagnostic tests have been developed, including
glasshouse pot assays, petri dish assays and chlorophyll fluorescence. A key
component of such tests is that the response of the suspect population to a
herbicide can be compared with that of known susceptible and resistant
standards under controlled conditions. Most cases of herbicide resistance are
a consequence of the repeated use of herbicides, often in association with
crop monoculture and reduced cultivation practices. It is necessary,
therefore, to modify these practices in order to prevent or delay the onset of
resistance or to control existing resistant populations. A key objective should
be the reduction in selection pressure. An integrated weed management
(IWM) approach is required, in which as many tactics as possible are used to
combat weeds. In this way, less reliance is placed on herbicides and so
selection pressure should be reduced.[76] In 2017, the USEPA issued a
revised Pesticide Registration Notice (PRN 2017-1), which provides guidance
to pesticide registrants on required pesticide resistance management
labeling. This requirement applies to all conventional pesticides and is meant
to provide end-users with guidance on managing pesticide resistance. [77]An
example of a fully executed label compliant with the USEPA resistance
management labeling guidance can be seen on the specimen label for the
herbicide, cloransulam-methyl, updated in 2022. [78]
Optimising herbicide input to the economic threshold level should avoid the
unnecessary use of herbicides and reduce selection pressure. Herbicides
should be used to their greatest potential by ensuring that the timing, dose,
application method, soil and climatic conditions are optimal for good activity.
In the UK, partially resistant grass weeds such as Alopecurus
myosuroides (blackgrass) and Avena genus (wild oat) can often be controlled
adequately when herbicides are applied at the 2-3 leaf stage, whereas later
applications at the 2-3 tiller stage can fail badly. Patch spraying, or applying
herbicide to only the badly infested areas of fields, is another means of
reducing total herbicide use.[76]
Approaches to treating resistant weedsEdit
Alternative herbicidesEdit
When resistance is first suspected or confirmed, the efficacy of alternatives
is likely to be the first consideration. The use of alternative herbicides which
remain effective on resistant populations can be a successful strategy, at
least in the short term. The effectiveness of alternative herbicides will be
highly dependent on the extent of cross-resistance. If there is resistance to a
single group of herbicides, then the use of herbicides from other groups may
provide a simple and effective solution, at least in the short term. For
example, many triazine-resistant weeds have been readily controlled by the
use of alternative herbicides such as dicamba or glyphosate. If resistance
extends to more than one herbicide group, then choices are more limited. It
should not be assumed that resistance will automatically extend to all
herbicides with the same mode of action, although it is wise to assume this
until proved otherwise. In many weeds the degree of cross-resistance
between the five groups of ALS inhibitors varies considerably. Much will
depend on the resistance mechanisms present, and it should not be
assumed that these will necessarily be the same in different populations of
the same species. These differences are due, at least in part, to the
existence of different mutations conferring target site resistance.
Consequently, selection for different mutations may result in different
patterns of cross-resistance. Enhanced metabolism can affect even closely
related herbicides to differing degrees. For example, populations
of Alopecurus myosuroides (blackgrass) with an enhanced metabolism
mechanism show resistance to pendimethalin but not to trifluralin, despite
both being dinitroanilines. This is due to differences in the vulnerability of
these two herbicides to oxidative metabolism. Consequently, care is needed
when trying to predict the efficacy of alternative herbicides. [76]

Mixtures and sequencesEdit

The use of two or more herbicides which have differing modes of action can
reduce the selection for resistant genotypes. Ideally, each component in a
mixture should:

 Be active at different target sites

 Have a high level of efficacy
 Be detoxified by different biochemical pathways
  Have similar persistence in the soil (if it is a residual herbicide)
 Exert negative cross-resistance
 Synergise the activity of the other component

No mixture is likely to have all these attributes, but the first two listed are
the most important. There is a risk that mixtures will select for resistance to
both components in the longer term. One practical advantage of sequences
of two herbicides compared with mixtures is that a better appraisal of the
efficacy of each herbicide component is possible, provided that sufficient
time elapses between each application. A disadvantage with sequences is
that two separate applications have to be made and it is possible that the
later application will be less effective on weeds surviving the first application.
If these are resistant, then the second herbicide in the sequence may
increase selection for resistant individuals by killing the susceptible plants
which were damaged but not killed by the first application, but allowing the
larger, less affected, resistant plants to survive. This has been cited as one
reason why ALS-resistant Stellaria media has evolved in Scotland recently
(2000), despite the regular use of a sequence incorporating mecoprop, a
herbicide with a different mode of action.[76]