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Herbicides and its applications.

The first widely used herbicide was 2,4-dichlorophenoxyacetic acid, often abbreviated 2,4-D. It was first commercialized by the Sherwin-Williams Paint Company and saw use in the late 1940s. It is easy and inexpensive to manufacture, and kills many broadleaf plants while leaving grasses largely unaffected (although high doses of 2,4-D at crucial growth periods can harm grass crops such as maize or cereals). 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 utilize either an amine salt (usually trimethylamine) or one of many esters of the parent compound. These are easier to handle than the acid.

2,4-D exhibits relatively good selectivity, meaning, in this case, that it controls a wide number of broadleaf weeds while causing little to no injury to grass crops at normal use rates. A herbicide is termed selective if it affects only certain types of plants, and nonselective if it inhibits a very broad range of plant types. Other herbicides have been more recently developed that achieve higher levels of selectivity than 2,4-D (Kellogg, 200).

The 1950s saw the introduction of the triazine family of herbicides, which includes atrazine, which have 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, frequently sold under the brand name Roundup, was introduced in 1974 for non-selective weed control. It is now a major herbicide in selective weed control in growing crop plants due to the development of crop plants that are resistant to it. 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 chemical herbicides for agriculture are specifically formulated to decompose within a short period after application. This is desirable as it allows crops which may be affected by the herbicide to be grown on the land in future seasons. However, herbicides with low residual activity (i.e., that decompose quickly) often do not provide season-long weed control (Kellogg, 2000).

Classification of Herbicides:

Herbicides can be classified by activity and uses. Classification by Activity:

* Contact herbicides destroy only the plant tissue in contact with the chemical. Generally, these are the fastest acting herbicides. They are less effective on perennial plants, which are able to regrow from rhizomes, roots or tubers.

* Systemic herbicides are translocated through the plant, either from foliar application down to the roots, or from soil application up to the leaves. They are capable of controlling perennial plants and may be slower acting but ultimately more effective than contact herbicides (Howard, 1992).

Classification by Uses:

* Pre-plant incorporated herbicides are soil applied prior to planting and mechanically incorporated into the soil. The objective for incorporation is to prevent dissipation through photodecomposition and/or volatility.

* Pre-emergent herbicides are applied to the soil before the crop emerges and prevent germination or early growth of weed seeds.Post-emergent herbicides are applied after the crop has emerged (Manolis, 1997).

Classification by Mechanism of Actions [MOA]:

Their classification by mechanism of action (MOA) indicates the first enzyme, protein, or biochemical step affected in the plant following application. The main mechanisms of action are:

* ACCase inhibitors are compounds that kill grasses. 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: the acetolactate synthase (ALS) enzyme (also known as acetohydroxyacid synthase, or AHAS) is 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 inhibition of DNA synthesis. They affect grasses and dicots alike. The ALS inhibitor family includes sulfonylureas (SUs), imidazolinones (IMIs), triazolopyrimidines (TPs), pyrimidinyl oxybenzoates (POBs), and sulfonylamino carbonyl triazolinones (SCTs). ALS is a biological pathway that exists only in plants and not in animals thus making the ALS-inhibitors among the safest herbicides.

* EPSPS inhibitors: The enolpyruvylshikimate 3-phosphate synthase enzyme EPSPS is used in the synthesis of the amino acids tryptophan, phenylalanine and tyrosine. They affect grasses and dicots alike. Glyphosate (Roundup) is a systemic EPSPS inhibitor but inactivated by soil contact.

* Synthetic auxin inaugurated the era of organic herbicides. They were discovered in the 1940s after a long study of the plant growth regulator auxin. Synthetic auxins mimic this plant hormone. They have several points of action on the cell membrane, and are effective in the control of dicot plants. 2,4-D is a synthetic auxin herbicide (Stryer, 1995). Photosystem II inhibitors reduce electron flow from water to NADPH2+ at the photochemical step in photosynthesis. They bind to the Qb site on the D1 protein, and prevent quinone from binding to this site. Therefore, this group of compounds causes electrons to accumulate on chlorophyll molecules. As a consequence, oxidation reactions in excess of those normally tolerated by the cell occur, and the plant dies. The triazine herbicides (including atrazine) and urea derivatives (diuron) are photosystem II inhibitors (Stryer, 1995).

Photosystem I inhibitors steal electrons from the normal pathway through FeS-Fdx-NADP leading to direct discharge of electrons on Oxygen. As result ROS (reactive oxygen species) are produced and oxidation reactions in excess of those normally tolerated by the cell occur leading to plant death. "Fe-S-Fdx step". Diphenilethers herbicides (like Nitrofen , Nitrofluorfen, Acifluoren) hit "Fdx-NADP step. ALS inhibitors: the acetolactate synthase (ALS) enzyme (also known as acetohydroxyacid synthase, or AHAS) is 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 inhibition of DNA synthesis. They affect grasses and dicots alike. The ALS inhibitor family includes sulfonylureas (SUs), imidazolinones (IMIs), triazolopyrimidines (TPs), pyrimidinyl oxybenzoates (POBs), and sulfonylamino carbonyl triazolinones (SCTs).

ALS is a biological pathway that exists only in plants and not in animals thus making the ALS-inhibitors among the safest herbicides (Stryer, 1995).

Classifification by Chemical Characteristics: Organic Herbicides:

Almost all herbicides in use today are considered "organic" herbicides in that they contain carbon as a primary molecular component. A notable exception would be the arsenical class of herbicides. Sometimes they are referred to as synthetic organic herbicides. Recently the term "organic" has come to imply products used in organic farming. Under this definition an organic herbicide is one that can be used in a farming enterprise that has been classified as organic. Organic herbicides are expensive and may not be affordable for commercial production They are much less effective than synthetic herbicides and are generally used along with cultural and mechanical weed control practices (Kolberg, 2002). Organic herbicides include:

* Spices are now effectively used in patented herbicides.

* Vinegar is effective for 5-20% solutions of acetic acid with higher concentrations most effective but mainly destroys surface growth and so respraying to treat regrowth is needed. Resistant plants generally succumb when weakened by respraying.

* Steam has been applied commercially but is now considered uneconomic and inadequate. It kills surface growth but not underground growth and so respraying to treat regrowth of perennials is needed (Kolberg, 2002).

* Flame is considered more effective than steam but suffers from the same difficulties.

* D-limonene (citrus oil). D-limonene (citrus oil) is a natural degreasing agent that strips the waxy skin or cuticle from weeds, causing dehydration and ultimately death.

Inorganic Herbicides:

Early chemical herbicides were inorganic compound. Herbicides such as ashes, common salts and bittern have been used in agriculture since ancient times.Inorganic herbicides is a chemical compound that kills plant or inhibits their normal growth .A herbicides in a particular formulation and application can be describe as selective or non selective. In agriculture, selective herbicides are often used instead of tillage, or in a combination with tillage other agronomic practices, to control without damaging crops. For these low-till or no-till systems, scientists are using biotechnology to develop crop varieties with increased tolerance for herbicides .Non selective herbicides, toxic to all plants are used where complete control of plant growth is required.Other popular inorganic herbicides includes; ammonium sulfamate, carbon bisulfide, sodium chlorate, sulfuric acid solutions and solutions and formulations containing borate.

Health and Enviromental Effects:

Herbicides have widely variable toxicity. In addition to acute toxicity from high exposures there is concern of possible carcinogenicity as well as other long-term problems such as contributing to Parkinson's disease. Parkinson's disease (also known as Parkinson's, Parkinson disease, or PD) is a degenerative disorder of the central nervous system that impairs motor skills, cognitive processes, and other functions. The most obvious symptoms are motor-related, including tremor, rigidity, slowness of movement, and postural instability. Among non-motor symptoms are autonomic dysfunction and sensory and sleep difficulties. Cognitive and behavioral problems, including dementia, are common in the advanced stages of the disease. PD usually appears around the age of 60, although there are young-onset cases (Howard, 1992).

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 labeled pre-harvest interval. Under extreme conditions herbicides can also be transported via surface runoff to contaminate distant water sources. Most herbicides decompose rapidly in soils via soil microbial decomposition, hydrolysis, or photolysis. Phenoxy herbicides are often contaminated with dioxins such as TCDD; research suggested that such contamination results in a small rise in cancer risk after exposure to these herbicides. Triazine exposure has been implicated in a likely relationship to increased risk of breast cancer, although a causal relationship remains unclear (Manolis, 1997; Stryer, 1995). Herbicide manufacturers have made bold and 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 (Kolberg, 2002).

Roundup is toxic and has resulted in death after being ingested in quantities ranging from 85-200 ml, although it has also been ingested in quantities as large as 500ml with only mild or moderate symptoms. The manfucturer of Tordon 101 (Dow AgroSciences, owned by the Dow Chemical Company) has claimed that Tordon 101 has no effects on animals and insects, in spite of evidence of strong carcinogenic activity of the active ingredient Picloram in studies on rats (Kolberg, 2002).

The risk of Parkinson's disease has been shown to increase with occupational exposure to herbicides and pesticides. The herbicide paraquat is suspected to be one environmental factor causing Parkinson's disease (Gorell, 1998; Dinis-Oliveira, 2006).

All organic and non-organic herbicides must be extensively tested prior to approval for commercial sale and labeling by the Environmental Protection Agency. However, because of the large number of herbicides in use, there is significant concern regarding health effects. In addition to health effects caused by herbicides themselves, commercial herbicide mixtures often contain other chemicals, including inactive ingredients, which have negative impacts on human health. For example, Roundup contains adjuvants which, even in low concentrations, were found to kill human embryonic, placental, and umbilical cells in vitro (Benachour, 2008). One study also found that Roundup caused genetic damage, but found that the damage was not caused by the active ingredient.

Some herbicides may have therapeutic uses. There is current research into the use of herbicides as an antimalaria drug that targets the plant-like apicoplast plastid in the malaria-causing parasite Plasmodium falciparum (Peluso, 1998).

Ecological Effects:

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 (Lawrence). Most observed effects are due not to toxicity but to habitat changes and the decrease in abundance of species birds rely on 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 are used which have low toxicity to birds, the herbicides decrease the abundance of many types of vegetation which the birds rely on. Herbicide use in agriculture in Britain has been linked to a decline in seed-eating bird species which rely on the weeds killed by the herbicides. 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 (MacKinnon, 1993; Ian Newton,; Robbins).

Scientific Uncertainty:

The health and environmental effects of many herbicides is unknown, and even within the scientific community there is often disagreement 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 that 2,4-D causes cancer in humans (Ibrahim, 1991). In 1992 there were too few studies on phenoxy herbicides 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's Lymphoma (Howard, 1992).

Classes of Some Common Herbicides: Glyphosate:

Glyphosate is an aminophosphonic analogue of the natural amino acid glycine, and the name is a contraction of gly(cine) phos(phon)ate. The molecule has several dissociable hydrogens, especially the first hydrogen of the phosphate group. The molecule tends to exist as a zwitterion where a phosphonic hydrogen dissociates and joins the amine group. Glyphosate is soluble in water to 12 g/L at room temperature. Glyphosate was first discovered to have herbicidal activity in 1970 by John E. Franz, while working for Monsanto. Franz received the National Medal of Technology in 1987, and the Perkin Medal for Applied Chemistry in 1990 for his discoveries.

In an editorial on May 17, 2010, the New York Times noted the appearance of glyphosate-resistant weeds (Alibhai, 2001; Richard, 2005; People, 1990).

Uses of Glyphosate:

Glyphosate is effective in killing a wide variety of plants, including grasses, broadleaf, and woody plants. It has a relatively small effect on some clover species. By volume, it is one of the most widely used herbicides. It is commonly used for agriculture, horticulture, and silviculture purposes, as well as garden maintenance (including home use) (Caviness, 1971; Shipitalo, 2008). Glyphosate is supplied in several formulations for different uses:

Ammonium salt, Isopropyl amine salt. Glyphosate acid-standalone, as ammonium salt or as isopropyl salt. Potassium salt

Products are supplied most commonly in formulations of 120, 240, 360, 480 and 680 g active ingredient per litre. The most common formulation in agriculture is 360 g, either alone or with added cationic surfactants. For 360 g formulations, European regulations allow applications of up to 12 litres per hectare for control of perennial weeds such as couch grass. More commonly, rates of 3 litres per hectare are practiced for control of annual weeds between crops (Johanns, 2005).

Effects of Glyphosate on Humans:

Glyphosate is rated least dangerous in comparison to other herbicides, such as those from the organochlorine family. Roundup has a United States Environmental Protection Agency (EPA) Toxicity Class of III (on a I to IV scale, where IV is least dangerous) for oral and inhalation exposure. It does not bioaccumulate, and breaks down rapidly in the environment (Chivian, 2008; U.S. EPA, 1993; Wojtaszek, 2004).

The United States Environmental Protection Agency considers glyphosate to be relatively low in toxicity, and without carcinogenic or teratogenic effects. The EPA considered a "worst case" dietary risk model of an individual eating a lifetime of food entirely from glyphosate-sprayed fields, and with residue levels remaining at their maximum levels, and concluded that no adverse effects would exist under these conditions In 2007, the EPA selected glyphosate for further screening for endocrinal disruptor effects (Balthazor, 1986; Fernandeza, 2005; Albers, 2009).

Laboratory toxicology studies suggest that other ingredients combined with glyphosate may have greater toxicity than glyphosate alone. For example, a study comparing glyphosate and Roundup found that Roundup had a greater effect on aromatase than glyphosate alone. Another study has shown that Roundup formulations and metabolic products cause the death of human embryonic, placental, and umbilical cells in vitro even at low concentrations. The effects are not proportional to Glyphosate concentrations but dependent on the nature of the adjuvants used in the formulation (Benachour, 2008).

Structure of Glyphosate:


2,4-diclorophenoxyacetic Acid:

2,4-Dichlorophenoxyacetic acid (2,4-D) is a common systemic herbicide used in the control of broadleaf weeds. It is the most widely used herbicide in the world, and the third most commonly used in North America. 2,4-D is a synthetic auxin (plant hormone), and as such it is often used in laboratories for plant research and as a supplement in plant cell culture media such as MS medium (Dichlorophenoxyacetic acid, 2,4- (2,4-D): 1989.).

Uses of 2,4-diclorophenoxyacetic Acid:

2,4-D is primarily used as a herbicide. It is sold in various formulations under a wide variety of brand names. 2,4-D can be found in lawn herbicide mixtures such as "Weed B Gon MAX", "PAR III", "Trillion", "Tri-Kil", "Killex" and "Weedaway Premium 3-Way XP Turf Herbicide". All of these mixtures typically contain three active ingredients: 2,4-D, mecoprop and dicamba. Over 1,500 herbicide products contain 2,4-D as an active ingredient (Suwa , 1996). 2,4-D is most commonly used for weed control in lawns and other turf, No2-till burndown, Control of weeds and brush along fences and highway and railroad rights of way, Conifer release (control of broad-leaf trees in conifer plantings), Grass hayfields and pastures, Cereal grains, Corn and sorghum (occasionally), and as a synthetic auxin analogue

2,4-D continues to be used, where legal, for its low cost. However, where municipal lawn pesticide bylaws exist, such as in Canada, alternatives such as corn gluten meal and vinegar-based products are increasingly being used to combat weeds (Jones, 2008).

Effects of 2,4-Diclorophenoxyacetic Acid:

Different organizations have taken different stances on 2,4-D's cancer risk. On August 8, 2007, the United States Environmental Protection Agency issued a ruling that stated that existing data does not support a conclusion that links human cancer to 2,4-D exposure. However, the International Agency for Research on Cancer (IARC) has classified 2,4-D among the phenoxy acid herbicides MCPA and 2,4,5-T as a class 2B carcinogen - possibly carcinogenic to humans. A 1995 panel of 13 scientists reviewing studies on the carcinogenicity of 2,4-D had divided opinions, but the predominant opinion was that it is possible that 2,4-D causes cancer in humans (Suwa, 1996; Jones, 2008; Ibrahim, 1991).

A 1990 study of farmers in Nebraska, even when adjusting for exposure to other chemicals, found that 2,4-D exposure substantially increased the risk of Non-Hodgkin's lymphoma (NHL). A 2000 study of 1517 former employees of Dow Chemical Company who had been exposed to the chemical in manufacturing or formulating 2,4-D found no significant increase in risk of mortality due to NHL following 2,4-D exposure, but did find an increase in risk of mortality due to amyotrophic lateral sclerosis (Zahm, 1990; Burnsa, 2001).

Structure of 2,4-dichlorophenoxyacetic Acid:



Atrazine, 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine, an organic compound consisting of an striazine-ring is a widely used herbicide. Its use is controversial due to widespread contamination in drinking water and its associations with birth defects, menstrual problems, and cancer when consumed by humans at concentrations below government standards. Although it has been excluded from a re-registration process in the European Union, it is still one of the most widely used herbicides in the world (Duhigg, 2009; "Chemicals, 2010).

Uses of Atrazine:

Atrazine is used to stop pre- and post-emergence broadleaf and grassy weeds in major crops. The compound is both effective and inexpensive, and thus is well-suited to production systems with very narrow profit margins, as is often the case with maize. Atrazine is the most widely used herbicide in conservation tillage systems, which are designed to prevent soil erosion.Its effect on yields has been estimated from 6% to 1%, with 3-4% being the conclusion of one review. In another study looking at combined data from 236 university corn field trials from 1986-2005, atrazine treatments showed an average of 5.7 bushels more per acre than alternative herbicide treatments (Ackerman, 2007; Fawcett, 2008).

Effects of Atrazine on Amphibians:

Atrazine is a suspected teratogen, causing demasculinization in male northern leopard frog even at low concentrations, and an estrogen disruptor. A 2010 study found that atrazine rendered 75 percent of male frogs sterile and turned one in 10 into females. A 2002 study found that exposure to atrazine caused male tadpoles to turn into hermaphrodites--frogs with both male and female sexual characteristics. But another study, requested by EPA and funded by Syngenta, was unable to reproduce these results (Fawcett, 2008; Jennifer, 2003; Tyrone, 2003; Mizota, 2006; Pesticide, 2010; Jooste et al., 2005).

Tyrone Hayes, Department of Integrative Biology, University of California, notes that all of the studies that failed to conclude that atrazine caused hermaphroditism were plagued by poor experimental controls and were funded by Syngenta, one of the companies that produce the chemical (Jooste et al., 2005). The U.S. Environmental Protection Agency (EPA) and its independent Scientific Advisory Panel (SAP) examined all available studies on this topic--including Hayes' work--and concluded that there are "currently insufficient data" to determine if Atrazine affects amphibian development. Hayes, formerly part of the SAP panel, resigned in 2000 to continue studies independently (Hayes, 2004). The EPA and its SAP made recommendations concerning proper study design needed for further investigation into this issue. As required by the EPA, Syngenta conducted two experiments under Good Laboratory Practices (GLP) and inspection by the EPA and German regulatory authorities. The paper concluded "These studies demonstrate that long-term exposure of larval X. laevis to atrazine at concentrations ranging from 0.01 to 100 microg/l does not affect growth, larval development, or sexual differentiation" (Bichat, 1999). Another independent study in 2008 determined that "the failure of recent studies to find that atrazine feminizes X. laevis calls into question the herbicide's role in that decline." A report written in Environmental Science and Technology (May 15, 2008) cites the independent work of researchers in Japan, who were unable to replicate Hayes' work. "The scientists found no hermaphrodite frogs; no increase in aromatase as measured by aromatase mRNA induction; and no increase in vitellogenin, another marker of feminization" (Briggs, 2002).

Structure of Atrazine:



Dicamba controls annual and perennial rose weeds in grain crops and highlands, and it is used to control brush and bracken in pastures, as well as legumes and cacti. It kills broadleaf weeds before and after they sprout. In combination with a phenoxyalkanoic acid or another herbicide, dicamba is used in pastures, range land, and noncrop areas (fence rows, roadways and wastage) to control weeds. Dicamba is toxic to conifer species but is generally less toxic to grasses (Crawford, 1998).

Dicamba functions by increasing plant growth rate. At sufficient concentrations, the plant outgrows its nutrient supplies, and dies.

The enzymes responsible for this first breakdown step is a three-component system called dicamba Odemethylase. One component of the three has recently been incorporated into the genome of a variety of crop plants making them resistant to dicamba (Mark, 2007).

Uses of Dicamba:

Dicamba is notorious for its ability to persist in dead plants and compost, and has accumulated to phytotoxic levels in finished compost in a few highly publicized cases. In Seattle, Washington, Dicamba was widely used for weed control in lawns until prohibited in 1999. There, a city-mandated curbside grass clipping collection and composting program produced compost with measurable levels of dicamba. Subsequently, DowAgro, the manufacturer of dicamba, voluntarily deregistered it for lawn uses.

Dicamba is still licensed for lawn use in France and is available under the following names: Bayer Jardin: Desherbant jeune gazon and Scanner Selectif gazon Vilmorin: desherbant Gazon LONPAR.

Effect of Dicamba:

Dicamba does not present unusual handling hazards. It is moderately toxic by ingestion and slightly toxic by inhalation or dermal exposure (oral LD50 in rats: 757 mg/kg body weight, dermal LD502,000 mg/kg, inhalation LC50200 mg/L) (Arnold, 2002). In a 3-generation study, dicamba did not affect the reproductive capacity of rats. When rabbits were given doses of 0, 0.5, 1, 3, 10 or 20 (mg/kg)/day of technical dicamba from days 6 through 18 of pregnancy, toxic effects on the mothers, slightly reduced fetal body weights, and increased loss of fetuses occurred at the 10 mg/kg dose. U.S. Environmental Protection Agency (EPA) has set the NOAEL for this study at 3 (mg/kg)/day. In dog tests, some enlargement of liver cells has occurred, but a similar effect has not been shown in man (Merck Index, 11th Edition, 3026).

Structure of Dicamba:



A Triazine is one of three organic chemicals, isomeric with each other, whose molecular formula is C3H3N3 and whose empirical formula is CHN.

Uses of Triazine:

The best known 1,3,5-triazine derivative is melamine with three amino substituents used in the manufacture of resins. Another triazine extensively used in resins is benzoguanamine. Triazine compounds are often used as the basis for various herbicides such as cyanuric chloride (2,4,6-trichloro-1,3,5-triazine). Chlorine-substituted triazines are also used as reactive dyes.

These compounds react through a chlorine group with hydroxyl groups present in cellulose fibres in nucleophilic substitution, the other triazine positions contain chromophores. Mixtures of Triazines and water are also used to remove H2S from natural gas.

A series of 1,2,4-triazine derivatives known as BTPs have been considered in the liquid-liquid extraction community as possible extractants for use in the advanced nuclear reprocessing of used fuel. BTPs are molecules containing a pyridine ring bonded to two 1,2,4-triazin8-3-yl groups (Benzoguanamine, 2000; Hansjuergen, 1956).

Effects of Triazine:

Although triazines are aromatic compounds, the resonance energy is much lower than in benzene and electrophilic aromatic substitution is difficult but nucleophilic aromatic substitution more frequent. 2,4,6Trichloro-1,3,5-triazine is easily hydrolyzed to cyanuric acid by heating with water at elevated temperatures. 2,4,6-Tris(phenoxy)-1,3,5-triazine reacts with aliphatic amines in aminolysis, and this reaction can be used to give dendrimers.

Pyrolysis of melamine under expulsion of ammonia gives the tri-s-triazine melem. Cyanuric chloride assists in the amidation of carboxylic acids (Christian, 2000).

The 1,2,4-triazines can react with electron-rich dienophiles in an inverse electron demand Diels-Alder reaction. This forms a bicyclic intermediate which normally then extrudes a molecule of nitrogen gas to form an aromatic ring again.

In this way the 1,2,4-triazines can be reacted with alkynes to form pyridine rings. An alternative to using an alkyne is to use norbornadiene which can be thought of as a masked alkyne (Barbara, 2003).

Structure of Triazine:



DL-Phosphinothricin is an herbicide commonly used in plant molecular biology and plant tissue culture. It is the ammonium salt of glufosinate. It is also known as Glufosinate or Glufosinate ammonium. The herbicide is a broad spectrum herbicide which is comparatively bio-degradable similar to glyphosate (Mayer, 2004). Glyphosate was first sold by Monsanto Company under the tradename Roundup, but is no longer under patent. Glufosinate is sold under trade names Basta, Buster and Liberty. Crops have been developed (genetically engineered) which are resistant to this herbicide through the insertion of the bar gene into plants.

Sructure of DL-Phosphinothricin:


Applications and Formulations of Herbicides:

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 a long boom, of 100 to 50 feet (30 to 15 m) with flat fan nozzles spaced about every 20 inches (510 mm). Towed, handheld, and even horse-drawn sprayers are also used. Synthetic organic herbicides can generally be applied aerially using helicopters or airplanes, and can be applied through irrigation systems (chemigation).

A new method of herbicide application involves ridding the soil of its active weed seed bank rather than just killing the weed. Researchers at the Agricultural Research Service have found that applying herbicides to fields late in the weed's growing season greatly reduces its seed production, and therefore fewer weeds will return the following season. If herbicides are applied at the correct stage in the weed's growing season, then the weed's presence in the soil seed bank will greatly be reduced. Because most weeds are annual grasses, their seeds will only survive in soil for a year or two, so this method will be able to "weed out" the weed with only a few years of herbicide application (Mayer, 2004). 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 plants. This allows treatment of taller grassland weeds by direct contact without affecting related but desirable plants in the grassland sward beneath.

Herbicides in Modern Usage:

* 2, 4-D, a broadleaf herbicide in the phenoxy group used in turf and in no-till field crop production. Now mainly used in a blend with other herbicides that allow lower rates of herbicides to be used, it is the most widely used herbicide in the world, third most commonly used in the United States. It is an example of synthetic auxin (plant hormone).

* Aminopyralid is a broadleaf herbicide in the pyridine group, used to control broadleaf weeds on grassland, such as docks, thistles and nettles. Notorious for its ability to persist in compost.

* Atrazine, a triazine herbicide used in corn and sorghum for control of broadleaf weeds and grasses. Still used because of its low cost and because it works extrodinarily well on a broad spectrum of weeds common in the U.S. corn belt, Atrazine is commonly used with other herbicides to reduce the over-all rate of atrazine and to lower the potential for groundwater contamination, it is a photosystem II inhibitor (Ackerman, 2007).

* Clopyralid is a broadleaf herbicide in the pyridine group, used mainly in turf, rangeland, and for control of noxious thistles. Notorious for its ability to persist in compost. It is another example of synthetic auxin.

* Dicamba, a post-emergent broadleaf herbicide with some soil activity, used on turf and field corn. It is another example of a synthetic auxin (Arnold, 2002).

* Glufosinate ammonium, a broad-spectrum contact herbicide and is used to control weeds after the crop emerges or for total vegetation control on land not used for cultivation.

* Fluroxypyr, a systemic, selective herbicide used for the control of broad-leaved weeds in small grain cereals, maize, pastures, range land and turf. It is a synthetic auxin. In cereal growing, fluroxypyr's key importance is control of cleavers, Galium aparine. Other key broad-leaved weeds are also controlled.

* Glyphosate, a systemic non-selective (it kills any type of plant) herbicide used in no-till burndown and for weed control in crops that are genetically modified to resist its effects. It is an example of an EPSPs inhibitor (Shipitalo, 2008).

* Imazapyr a non-selective herbicide used for the control of a broad range of weeds including terrestrial annual and perennial grasses and broadleaved herbs, woody species, and riparian and emergent aquatic species.

* Imazapic, a selective herbicide for both the pre- and post-emergent control of some annual and perennial grasses and some broadleaf weeds. Imazapic kills plants by inhibiting the production of branched chain amino acids (valine, leucine, and isoleucine), which are necessary for protein synthesis and cell growth.

* Linuron is a non-selective herbicide used in the control of grasses and broadleaf weeds. It works by inhibiting photosynthesis.

Historical Interest of 2,4,5-Trichlorophenoxyacetic Acid:

2,4,5-Trichlorophenoxyacetic acid (2,4,5-T) was a widely used broadleaf herbicide until being phased out starting in the late 1970s. While 2,4,5-T itself is of only moderate toxicity, the manufacturing process for 2,4,5T contaminates this chemical with trace amounts of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). TCDD is extremely toxic to humans. With proper temperature control during production of 2,4,5-T, TCDD levels can be held to about .005 ppm. Before the TCDD risk was well understood, early production facilities lacked proper temperature controls. Individual batches tested later were found to have as much as 60 ppm of TCDD.

2,4,5-T was withdrawn from use in the USA in 2011, at a time of heightened public sensitivity about chemical hazards in the environment. Public concern about dioxins was high, and production and use of other (non-herbicide) chemicals potentially containing TCDD contamination was also withdrawn. These included pentachlorophenol (a wood preservative) and PCBs (mainly used as stabilizing agents in transformer oil). Some feel that the 2,4,5-T withdrawal was not based on sound science. 2,4,5-T has since largely been replaced by dicamba and triclopyr.

Agent Orange was a herbicide blend used by the U.S. military in Vietnam between January 1965 and April 1970 as a defoliant. It was a 50/50 mixture of the n-butyl esters of 2,4,5-T and 2,4-D. Because of TCDD contamination in the 2,4,5-T component, it has been blamed for serious illnesses in many veterans and Vietnamese people who were exposed to it. However, research on populations exposed to its dioxin contaminant has been inconsistent and inconclusive. Agent Orange often had much higher levels of TCDD than 2,4,5-T used in the US. The name Agent Orange is derived from the orange color-coded stripe used by the Army on barrels containing the product. It is worth noting that there were other blends of synthetic auxins at the time of the Vietnam War whose containers were recognized by their colors, such as Agent Purple and Agent Pink.

Control of Weeds with Specific Herbicides:
                     Weeds Controlled with Velpar

Grasses              Bushes and Srubs             Other Weeds

Kentucky bluegrass   Bristly sarsaparilla Sheep   Tall white aster
                     laurel (lambkill) Birch
Soft rush            Willow *                     Mouse-eared hawkweed
Black sedge          Hardhack                     Rough goldenrod
Witchgrass           Poplar                       Large-leaved
Browntop             Trailing blackberry *        Five-fingered
                                                  cinquefoil *
Creeping bentgrass   Rhodora                      Stitchwort
Wood rush *          Wild Raspberry               Sheep-sorrel
Poverty oat grass    Meadow-sweet                 Cow wheat *
Sweet vernal grass                                Yarrow
Hair fescue                                       Purple aster
                                                  King devil hawkweed
                                                  Canada goldenrod
                                                  Wild strawberry
                                                  Orange hawkweed
                                                  Pearly everlasting
Creeping bentgrass                                Large-leaved
                                                  goldenrod *
Sweet vernal grass                                Mouse-eared hawkweed
Kentucky bluegrass                                King devil hawkweed
Witchgrass                                        Five-fingered
                                                  cinquefoil *
Hair fescue                                       Wild strawberry
Poverty oatgrass                                  Orange hawkweed
* Browntop                                        Canada goldenrod *
                                                  Rough goldenrod
                                                  Purple aster
                                                  Yarrow *

These tables are provided as a guide only. Control will vary depending on the conditions in the field. This table is not an intended as an endorsement of any specific product. Not all weeds are listed in the table. For a more complete list of weeds controlled with these products, see "Weeds of Eastern Canadian Blueberry Fields".


This study has shown that herbicides are chemical substances because of their chemical composition and are also referred to as economic substances because they unite and are majorly used on agricultural farm. While some herbicides are naturally supplied (walnut), others are artificial such as 2,4-dichlorophenoxyacetic acid and Atrazine. These various classes of Herbicides have different physical and chemical properties that gives them value and usefulness under their own class.


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Corresponding Author: Hamid, A.A., Department of Chemistry, University of Ilorin, P.M.B. 1515, Ilorin-Nigeria. Phone: +2347035931646 E-mail:;;

(1) Hamid, A.A., (2) Aiyelaagbe, O.O. and (1) Balogun, G.A.

(1) Department of Chemistry, University of Ilorin, P.M.B. 1515, Ilorin-Nigeria.

(2) Department of Chemistry, University of Ibadan, Ibadan-Nigeria.
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Title Annotation:Original Article
Author:Hamid, A.A.; Aiyelaagbe, O.O.; Balogun, G.A.
Publication:Advances in Natural and Applied Sciences
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Date:Apr 1, 2011
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