Herbicides (, ), also commonly known as weed killers, are substances used to control undesired plants, also known as weeds.EPA. February 2011 Pesticides Industry. Sales and Usage 2006 and 2007: Market Estimates . Summary in press release here Main page for EPA reports on pesticide use is here. Selective herbicides control specific weed species while leaving the desired crop relatively unharmed, while non-selective herbicides (sometimes called "total weed killers") kill plants indiscriminately. The combined effects of herbicides, nitrogen fertilizer, and improved cultivars has increased yields (per acre) of major crops by three to six times from 1900 to 2000.
In the United States in 2012, about 91% of all herbicide usage was, determined by weight, applied in agriculture. In 2012, world pesticide expenditures totaled nearly US$24.7 billion; herbicides were about 44% of those sales and constituted the biggest portion, followed by insecticides, fungicides, and fumigants. Herbicide is also used in forestry, where certain formulations have been found to suppress hardwood varieties in favor of conifers after clearcutting, as well as pasture systems.
History Prior to the widespread use of herbicides, cultural controls, such as altering soil pH, salinity, or fertility levels, were used to control weeds. Mechanical control including tillage and flooding were also used to control weeds. In the late 19th and early 20th centuries, inorganic chemicals such as sulfuric acid, arsenic, copper salts, kerosene and sodium chlorate were used to control weeds, but these chemicals were either toxic, flammable or corrosive and were expensive and ineffective at controlling weeds.
First herbicides
The major breakthroughs occurred during the Second World War as the result of research conducted independently in the United Kingdom and the United States into the potential use of herbicides in war. The compound 2,4-D was first synthesized by W. G. Templeman at Imperial Chemical Industries. In 1940, his work with indoleacetic acid and naphthaleneacetic acid indicated that "growth substances applied appropriately would kill certain broad-leaved weeds in cereals without harming the crops," though these substances were too expensive and too short-lived in soil due to degradation by microorganisms to be of practical agricultural use; by 1941, his team succeeded in synthesizing a wide range of chemicals to achieve the same effect at lower cost and better efficacy, including 2,4-D. In the same year, R. Pokorny in the US achieved this as well. 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.
When 2,4-D was commercially released in 1946, it became the first successful selective herbicide, triggering a worldwide revolution in agricultural output. 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.
Further discoveries 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 had been first prepared in the 1950s but its herbicidal activity was only recognized in the 1960s. It was marketed as Roundup in 1971. Since 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 degrade within a short period after application.
Terminology Herbicides can be classified/grouped in various ways; for example, according to their activity, the timing of application, method of application, mechanism of their action, and their chemical structures.
Selectivity Chemical structure of the herbicide is of primary affecting efficacy. 2,4-D, mecoprop, and dicamba control many broadleaf weeds but remain ineffective against turf grasses.
Chemical additives influence selectivity. Surfactants alter the physical properties of the spray solution and the overall phytotoxicity of the herbicide, increasing translocation. Herbicide safeners enhance the selectivity by boosting herbicide resistance by the crop but allowing the herbicide to damage the weed.
Selectivity is determined by the circumstances and technique of application. Climatic factors affect absorption including humidity, light, precipitation, and temperature. Foliage-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 can interfere with absorption. Precipitation may wash away or remove some foliage-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.
Non-selective herbicides Non-selective herbicides, generally known as defoliants, are used to clear industrial sites, waste grounds, railways, and railway embankments. Paraquat, glufosinate, and glyphosate are non-selective herbicides.
Timing of application 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. 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. 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. 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.
Method of application 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. 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.
Persistence 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.
Mechanism of action
Herbicides interfere with the biochemical machinery that supports plant growth. Herbicides often mimic natural plant hormones, enzyme substrates, and cofactors. They interfere with the metabolism in the target plants. Herbicides are often classified according to their site of action because as a general rule, herbicides within the same site of action class produce similar symptoms on susceptible plants. Classification based on the site of action of the herbicide is preferable as herbicide resistance management can be handled more effectively. Classification by mechanism of action (MOA) indicates the first enzyme, protein, or biochemical step affected in the plant following application:
ACCase inhibitors: Acetyl coenzyme A carboxylase (ACCase) is part of the first step of lipid synthesis. Thus, ACCase inhibitors affect cell membrane production in the meristems of the grass plant. The ACCases of grasses are sensitive to these herbicides, whereas the ACCases of dicot plants are not. ALS inhibitors: Acetolactate synthase (ALS; also known as acetohydroxyacid synthase, or AHAS) is part of the first step in the synthesis of the branched-chain amino acids (valine, leucine, and isoleucine). These herbicides slowly starve affected plants of these amino acids, which eventually leads to the inhibition of DNA synthesis. They affect grasses and dicots alike. The ALS inhibitor family includes various sulfonylureas (SUs) (such as flazasulfuron and metsulfuron-methyl), imidazolinones (IMIs), triazolopyrimidines (TPs), pyrimidinyl oxybenzoates (POBs), and sulfonylamino carbonyl triazolinones (SCTs). The ALS biological pathway exists only in plants and microorganisms (but not animals), thus making the ALS-inhibitors among the safest herbicides.