Classification of the household hazardous products.
\\n\\n
Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\\n\\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'IntechOpen is proud to announce that 179 of our authors have made the Clarivate™ Highly Cited Researchers List for 2020, ranking them among the top 1% most-cited.
\n\nThroughout the years, the list has named a total of 252 IntechOpen authors as Highly Cited. Of those researchers, 69 have been featured on the list multiple times.
\n\n\n\nReleased this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\n\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
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She is currently an assistant professor in the Department\nof English Studies at Complutense University of Madrid, and a\nmember of the research groups Studies on Intermediality and\nIntercultural Mediation (SIIM-UCM) and Biopoetics, Cognitive\nSemiotics and Neuroesthetics (IUIBS-ULPGC). Her academic\ninterests revolve around the new cognitive studies in neuroesthetics, semiotics, and\nnarratology. 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Her research interests are comparative literature, cultural and education studies, and cognitive and intermedial semiotics. In 2007 she established the Research Program Studies on Intermediality and Intercultural Mediation (SIIM), which has received funding from various sources for several projects. She is an external evaluator in various research programs of the European Commission and other national agencies (the Netherlands Organisation for Scientific Research (NWO) and the German Academic Exchange Service (DAAD), etc.). She is also an editor of several journals in her research areas. She has served as the President of the European Society of Comparative Literature and Deputy Head of the English Department at Complutense.",institutionString:"Complutense University of Madrid",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"2",totalChapterViews:"0",totalEditedBooks:"3",institution:{name:"Complutense University of Madrid",institutionURL:null,country:{name:"Spain"}}},coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"238",title:"Psycholinguistics",slug:"psycholinguistics"}],chapters:[{id:"72178",title:"Cognitive Semiotics and Conceptual Blend: A Case Study from The Crying of Lot 49",slug:"cognitive-semiotics-and-conceptual-blend-a-case-study-from-em-the-crying-of-lot-49-em-",totalDownloads:171,totalCrossrefCites:0,authors:[{id:"302728",title:"Dr.",name:"Marta",surname:"Silvera-Roig",slug:"marta-silvera-roig",fullName:"Marta Silvera-Roig"}]},{id:"69940",title:"Semiotic Principles in Cognitive Neuroscience",slug:"semiotic-principles-in-cognitive-neuroscience",totalDownloads:345,totalCrossrefCites:0,authors:[{id:"146731",title:"Dr.",name:"Edna",surname:"Andrews",slug:"edna-andrews",fullName:"Edna Andrews"}]},{id:"69515",title:"Analog, Embodiment, and Freedom",slug:"analog-embodiment-and-freedom",totalDownloads:375,totalCrossrefCites:0,authors:[{id:"308016",title:"Dr.",name:"Ted",surname:"Gemberling",slug:"ted-gemberling",fullName:"Ted Gemberling"}]},{id:"69023",title:"‘Evolutionary Stories’: Narratives as Evolutionary Tools to Describe and Analyse Animal Behaviour and Animal Signals",slug:"-evolutionary-stories-narratives-as-evolutionary-tools-to-describe-and-analyse-animal-behaviour-and-",totalDownloads:242,totalCrossrefCites:1,authors:[{id:"305894",title:"Dr.",name:"Gabriel",surname:"Francescoli",slug:"gabriel-francescoli",fullName:"Gabriel Francescoli"}]},{id:"70557",title:"Assessment of Perception of Physical Environment in the Context of Cognitive Maps and Experiences",slug:"assessment-of-perception-of-physical-environment-in-the-context-of-cognitive-maps-and-experiences",totalDownloads:248,totalCrossrefCites:0,authors:[{id:"311341",title:"Dr.",name:"Orkun",surname:"Alptekin",slug:"orkun-alptekin",fullName:"Orkun Alptekin"},{id:"311563",title:"Dr.",name:"Hasan",surname:"Unver",slug:"hasan-unver",fullName:"Hasan Unver"}]},{id:"69692",title:"Semiotic Architecture of Viral Data",slug:"semiotic-architecture-of-viral-data",totalDownloads:212,totalCrossrefCites:0,authors:[{id:"303983",title:"Dr.",name:"Berna",surname:"Valle",slug:"berna-valle",fullName:"Berna Valle"},{id:"303984",title:"Dr.",name:"Cesar",surname:"Chavarria",slug:"cesar-chavarria",fullName:"Cesar Chavarria"}]},{id:"70097",title:"Sources of Computer Metaphors for Visualization and Human-Computer Interaction",slug:"sources-of-computer-metaphors-for-visualization-and-human-computer-interaction",totalDownloads:242,totalCrossrefCites:0,authors:[{id:"135209",title:"Prof.",name:"Vladimir",surname:"Averbukh",slug:"vladimir-averbukh",fullName:"Vladimir Averbukh"}]},{id:"70553",title:"The Biolinguistic Instantiation: Form to Meaning in Brain/Syllable Interactions",slug:"the-biolinguistic-instantiation-form-to-meaning-in-brain-syllable-interactions",totalDownloads:217,totalCrossrefCites:0,authors:[{id:"305735",title:"Dr.",name:"Noury",surname:"Bakrim",slug:"noury-bakrim",fullName:"Noury Bakrim"}]},{id:"70186",title:"Computational Model for the Construction of Cognitive Maps",slug:"computational-model-for-the-construction-of-cognitive-maps",totalDownloads:218,totalCrossrefCites:4,authors:[{id:"299703",title:"Dr.",name:"Larisa",surname:"Ismailova",slug:"larisa-ismailova",fullName:"Larisa Ismailova"},{id:"299704",title:"Prof.",name:"Viacheslav",surname:"Wolfengagen",slug:"viacheslav-wolfengagen",fullName:"Viacheslav Wolfengagen"},{id:"299711",title:"Mr.",name:"Sergey V.",surname:"Kosikov",slug:"sergey-v.-kosikov",fullName:"Sergey V. Kosikov"}]}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"247041",firstName:"Dolores",lastName:"Kuzelj",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/247041/images/7108_n.jpg",email:"dolores@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. 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These wastes have the potential to cause irreversible damage to public health and other living organisms when disposed into the environment without proper treatment. Greater risks are often posed by hazardous substances to the environment and public health than nonhazardous substances. Therefore, it requires a strict control regime. HHWs have a significant adverse effect on public health, other living organisms, and the environment because of their inherent toxic, chemical, and physical characteristics at low concentration [2]. Therefore, these types of waste stream require stringent control and management in order to protect the environment and human health from potential negative impacts. Although HHWs only make up a small percentage of household wastes in general, they are considered to be potentially harmful [3].
\nThe WRc [4] defines HHWs as “such wastes that could potentially increase the hazardous properties of municipal solid waste when landfilled, incinerated or composted.” HHWs can also be described as leftovers from household products containing corrosive, toxic, ignitable, or reactive ingredients [5, 6]. The National Household Hazardous Waste Forum (NHHWF) in the United Kingdom defined HHW as “any discarded material by a household, which is difficult to dispose of, or which puts human health or the environment at risk because of its chemical or biological nature” [7]. Certain types of HHWs may pose potential physical injuries to sanitation workers, contaminate septic tanks, or wastewater treatment systems if poured down drains or toilets. They can also present hazards to children and pets if left around the house unattended [1].
\nHHWs must be separated from other domestic wastes and should not be disposed of together with municipal wastes because they require special treatment before disposal. They are harmful and are potential risks to humans [1]. HHWs vary in forms; some exists as liquids, solid, and gases making their treatment and management a bit complex. The list of HHWs differs between countries. Common examples include pesticides, paints (latex, nonlatex antialgae), motor oil, vanishes, antifreeze, various types of batteries (such as laptop batteries, car batteries, cellphone batteries), fluorescent light bulbs, fertilizers, thermometers, thermostats, solvents, unused medicines, bathroom and tile cleaners, brake fluid, asbestos, household cleaners (spot remover, degreaser, oven cleaner), stain, adhesives, lead acid, used gasoline, polish, wax, several electronics (such as television, computers, radio, and cellphones), photographic chemicals, flea powders, insect repellents, polish, rodent control, fabric, transmission fluid, and microfilm [1, 5–11]. The above examples of HWWs contain hazardous ingredients and require special attention for their disposal and treatment.
\nImproper disposal of HHW may change the way the biosphere functions, depletes the ozone layer and causes irreversible damage to domestic water sources. This could result in reduction of the productivity of global ecosystems at a time when millions of people are looking for livelihoods and sustenance to be provided by the environment [12]. For several reasons ranging from inadequate knowledge, lack of educational campaigns, lack of awareness on the impacts of HHWs and financial mismanagement are responsible for their improper disposal. HHW management is not usually given priority in most developing countries of the world, priority is mostly given to poverty alleviation, unemployment, and other economic problems. HHWs are usually disposed of with other domestic wastes such as disposal in drains, on the ground, into storm sewers, or in some cases with regular trash (Figure 1). Hence, HHW management, including disposal and recycling, seems to be urgent especially in the developing countries (sub‐Saharan Africa) where domestic waste management technologies are still limited.
\nHousehold hazardous wastes discarded in the trash may ignite or explode in the collection truck. Trash collectors may be injured from fumes and splashing chemicals. In landfills, leachate from the waste pollutes soil, surface water, and groundwater aquifers [4]. Disposal of hazardous household wastes in drains might also pollute drinking water [5]. In septic systems, hazardous wastes can kill the organisms that make the system work [3]. This may cause the bulk of untreated wastes to drain into the soil and eventually seep into the groundwater. Sewage treatment systems such as septic systems can be contaminated by improper disposal of hazardous household wastes [2–5, 13]. Due to the danger and risk posed by household hazardous wastes, good practices of handling, treatment, and disposal of these wastes should ideally begin in the household [1, 5, 14].
\nThe use of materials with hazardous ingredient is likely to increase in sub‐Saharan Africa due to increased industrialization and population growth [15–17]. If industrial and population growth is not balanced with efficient interventions to manage HHWs, most surface and groundwater sources are prone to varying degrees of pollution, some of which is irreversible. The effects of inadequate disposal of HHWs are not usually felt at the time of disposal, but with time, they pose significant risks to users of the resource further downstream [16, 17]. Most constituents of HHWs are persistent in nature and nonbiodegradable; once released into the environment, they transform from one form into a more toxic form [5, 9, 11]. Fauziah and Agamuthu [15] stated that one of the reasons for inadequate disposal and management of HHWs is inadequate awareness among the public as hazardous waste such as medicines, clinical bandages, and batteries that are commonly found in the refuse sent to landfill. This is one of the reasons why high concentrations of heavy metals are often detected in landfill leachate [16].
\nIllegal disposal of solid waste with HHW in different countries in sub‐Saharan Africa.
Household chemicals—a subset of hazardous wastes—are contaminants that are released during the use of various products in daily life. Several studies indicate that indoor air pollution is far worse than that of outdoor because homes, for energy efficiency, are made somewhat airtight [17, 18]. Moreover, household chemicals are trapped in houses causing further deterioration of indoor air quality. Household hazardous chemicals are potentially dangerous chemicals that can be found within households [19]. Some very important products needed for comfortable living in various households contain hazardous ingredients. Hazardous products generally divided into six groups as shown in Table 1 [17]. Household hazardous products may cause health and environmental problems to their users and when disposed into the environment. If the unwanted portions of these products go down the drain, into the trash, or get burned, they may cause harm to the environment.
\nClass | \nHazardous products | \nExamples | \n
---|---|---|
I | \nAutomotive products | \nGasoline, motor oil, brake fluid, wiper fluid, hydraulic oil, and car batteries | \n
II | \nHome improvement products | \nPaint (oil‐based and latex), caulk, varnish, air freshener | \n
III | \nHealth and beauty products | \nNail polish, finger nail polish remover, nail varnish, hair dye, bath salts/bubble bath, and skin creams | \n
IV | \nPesticides | \nRat poison, flea killer, insecticide, fungicide, moth balls, ant poison, and herbicide | \n
V | \nHousehold cleaners | \nFurniture polish, oven cleaner, toilet bowl cleaner, scouring agent, shoe polish, stain remover, disinfectant, and bleach | \n
VI | \nMiscellaneous items | \nFabric dyes, fluorescent tubes, low energy light bulbs, ink cartridge and toner, glue, antifreeze, and among others. | \n
Classification of the household hazardous products.
As stated earlier, household products are considered hazardous if they are radioactive, have dangerous biological characteristics, toxic, or flammable [6]. Many hazardous products have more than one of these hazardous characteristics. Corrosive substances destroy metal surfaces and living tissues and have the ability to chemically change whatever they come in contact with. Corrosive substances are acidic (pH less than or equal to 2) or caustic (pH higher than or equal to 12.5) [20]. Reactive substances are very unstable and interact with the substances around them. They are explosive and can sometimes create toxic fumes. Flammable substances will burst into flames if they come into contact with sparks or flames at certain temperatures. The temperature at which this occurs is referred to as the flash point. Flammable liquids have a flash point of 60°C [21]. Toxic substances cause immediate or long-term negative health problems. Exposure to toxic materials may result in injury, illness, or death [21, 22].
\nThe effects of hazardous substances on humans and other organisms vary greatly [23–26]. This often depends on the extent of exposure, the concentration of the substance, the nature of the hazardous substance, and the unique characteristics of individuals [20, 21]. The characteristics that influence toxicity of a substance include:\n
Genetic factors: For example, the efficiency of the kidney can affect the ability to excrete toxins.
Lifestyle of the individual: Smoking, alcohol consumption, obesity, and previous medical history all affect how the body reacts to toxins. In general, healthier individuals are able to fend off some toxins.
Gender: Some toxins have different effects on males and females. Generally, women have a larger percentage of fat in their total body weight, meaning they can accumulate more fat soluble toxins in their bodies than men.
Age: Old and very young people are more vulnerable to the effects of toxic substances. Because infants and young children (less than 5 years old) have underdeveloped immune systems, they are the most susceptible to HHWs. In addition, because children have high respiration rates, they are more susceptible to toxins through inhalation.
Allergic sensitivity: Individuals who are particularly sensitive to chemicals will experience allergic reaction to some toxic chemicals at low concentrations.
Table 2 presents some household products and their hazardous components as well as the potential health hazards. The health risks associated with HHWs are numerous and these substances must be managed appropriately in order to prevent possible risks to public health.
\nProduct type | \nClass | \nHazardous components | \nHazardous status | \nPotential health hazards | \n
---|---|---|---|---|
1. Air fresheners and deodorizers | \nII | \nFormaldehyde | \nToxic flammable | \nCarcinogen; irritates eyes, nose, throat, and skin; nervous, digestive, respiratory system damage | \n
2. Bleach | \nV | \nSodium hypochlorite | \nCorrosive toxic | \nIrritates and burns skin and eyes; nervous, respiratory, digestive system damage | \n
3. Disinfectants | \nV | \nSodium hypochlorite | \nCorrosive toxic | \nIrritates and burns skin and eyes; nervous, respiratory, digestive system damage | \n
\n | \n | Phenols | \nToxic flammable | \nRespiratory and circulatory system damage. | \n
\n | \n | Ammonia | \nToxic | \nVapor irritates skin, eyes and respiratory tract | \n
4. Drain cleaner | \nV | \nSodium/potassium hydroxide | \nCorrosive toxic | \nBurns skin and eyes; nervous, digestive and urinary system damage | \n
5. Flea powder | \nIV | \nCarbaryl | \nToxic | \nIrritates skin; causes nervous, respiratory and circulatory system damage | \n
\n | \n | Dichlorophene | \nToxic | \nIrritates skin; causes nervous and digestive system damage | \n
\n | \n | Chlordane and other chlorinated hydrocarbons | \nToxic | \nIrritates eyes and skin; cause respiratory, digestive and urinary system damage | \n
6. Floor cleaner/wax | \nV | \nDiethylene glycol | \nToxic | \nCauses nervous, digestive and urinary system damage | \n
\n | \n | Petroleum solvents | \nFlammable | \nCarcinogenic; irritate skin, eyes, throat, nose and lungs | \n
\n | \n | Ammonia | \nToxic | \nVapor irritates skin, eyes and respiratory tract | \n
7. Furniture polish | \nV | \nPetroleum distillates or mineral spirits | \nFlammable toxic | \nCarcinogen; irritates skin, eyes, nose, throat and lungs | \n
8. Oven cleaner | \nV | \nSodium/potassium hydroxide | \nCorrosive toxic | \nBurns skin, eyes; causes nervous and digestive system damage | \n
9. Paint thinner | \nIII | \nChlorinated aliphatic hydrocarbons | \nToxic | \nCause digestive and urinary system damage | \n
\n | \n | Esters | \nToxic | \nIrritates eyes, nose, and throat | \n
\n | \n | Alcohols | \nFlammable | \nCause nervous system damage; irritate eyes, nose, and throat | \n
\n | \n | Chlorinated aromatic hydrocarbons | \nFlammable toxic | \nDigestive system damage | \n
10. Paints | \nII | \nKetones | \nFlammable toxic | \nRespiratory system damage | \n
\n | \n | Aromatic hydrocarbon thinners | \nFlammable toxic | \nCarcinogenic; irritates skin, eyes, nose and throat; respiratory system damage | \n
\n | \n | Mineral spirits | \nFlammable toxic | \nIrritates skin, eyes, nose and throat; respiratory system damage | \n
11. Pool sanitizers | \nV | \nCalcium hypochlorite | \nCorrosive | \nIrritates skin, eyes, and throat; if ingested cause severe burns to the digestive tract | \n
\n | \n | Ethylene (algaecides) | \nFlammable toxic | \nIrritation of eyes, mucous membrane and skin; effects reproductive system; probable human carcinogen of medium carcinogenic hazard | \n
12. Toilet bowl cleaner | \nV | \nSodium acid sulfate or oxalate or hypochloric acid | \nCorrosive toxic | \nBurns skin; causes digestive and respiratory system damage | \n
\n | \n | Chlorinated phenols | \nFlammable toxic | \nCause respiratory and circulatory system damage. | \n
13. Window cleaners | \nV | \nDiethylene glycol | \nToxic | \nCause nervous, urinary and digestive system damage | \n
\n | \n | Ammonia | \nToxic | \nVapor irritates skin, eyes and respiratory tract. | \n
14. Motor oil | \nI | \nHeavy metals | \nToxic | \nCan cause nerve and kidney damage; is thought to cause cancer | \n
\n | \n | Hydrocarbons | \nFlammable | \nSome forms thought to cause cancer | \n
15. Batteries (car, boat, tractor) | \nVI | \nSulfuric acid | \nToxic corrosive | \nCan cause severe skin burns, and blindness | \n
\n | \n | Lead | \nToxic corrosive | \nCan cause nerve and kidney damage; is thought to cause cancer | \n
16. Windshield washer fluid | \nI | \nMethanol | \nFlammable toxic | \nCan damage the nervous system, liver, kidneys; inhalation can lead to lung disease; ingestion can cause blindness | \n
\n | \n | Ethylene glycol | \nFlammable toxic | \nCan cause severe damage to heart, kidneys, and brain. Inhalation can cause dizziness | \n
\n | \n | Isopropanol | \nFlammable | \nCan irritate mucous membranes; ingestion results in drowsiness, unconsciousness and death | \n
17. Laundry detergent | \nV | \nCationic, anionic, or nonionic solutions | \nReactive | \nIf swallowed, cationic detergents can cause nausea, vomiting, shock, convulsions, and coma. Nonionic detergents can irritate skin and eyes | \n
18. All‐purpose cleaners | \nV | \nAmmonia | \nToxic | \nFumes can irritate eyes and lungs; can cause burns or rashes on skin; can produce deadly chloramine gas if mixed with chlorine‐containing products | \n
\n | \n | Ethylene glycol monobutyl acetate | \nFlammable toxic | \nCan cause severe damage to heart, kidneys, brain. Inhalation can cause dizziness | \n
\n | \n | Sodium hypochlorite | \nCorrosive | \nCorrosive to skin and lining of nose mouth and throat; fumes irritating to eyes and respiratory tract | \n
19. Pet flea and tick treatments | \nIV | \nOrganophosphates and carbamates | \nToxic | \nCan cause headache, dizziness, twitching, nausea; known to cause cancer in animals | \n
20. Insecticides | \nIV | \nOrganophosphates and carbamates | \nToxic | \nCan cause headache, dizziness, twitching, nausea; known to cause cancer in animals | \n
21. Household foggers | \nIV | \nPyrethrins | \nToxic | \nCan cause severe allergic dermatitis, systemic allergic reactions. Large amounts may cause nausea, vomiting, tinnitus, headache, & other CNS disturbances | \n
\n | \n | Permethrin | \nToxic | \nCan cause itching and burning of the skin and eyes; irritates the upper respiratory tract | \n
\n | \n | Methoprene | \nToxic | \nCan irritate the skin and eyes | \n
22. Swimming pool chloride tablets | \nII | \nSodium (or calcium) hypochlorite | \nCorrosive reactive | \nCorrosive to skin and lining of nose mouth and throat; fumes irritating to eyes and respiratory tract | \n
23. Insect repellants | \nIV | \nButopyronoxyl | \nToxic | \nCan cause mild necrosis in liver and kidney –in animals | \n
\n | \n | Dimethyl phthalate | \nToxic | \nCan cause central nervous system depression if swallowed | \n
\n | \n | Diethyltoluamide (DEET) | \nToxic | \nCan irritate sensitive skin and respiratory tract tissues as well as loss of coordination, anxiety, behavioral changes, and mental confusion | \n
24. Weed killers | \nIV | \nDiquat, 2,4‐D, and glyphosate | \nToxic | \nCan irritate the eyes and skin; can cause abdominal pain, nausea, vomiting, and diarrhea | \n
25. Rodent control | \nIV | \nWarfarin | \nReactive | \nCauses internal bleeding if ingested in large amounts | \n
26. Rug, carpet, upholstery cleaners | \nV | \nPerchloroethylene | \nToxic | \nFumes cause dizziness, sleepiness, nausea, loss of appetite and disorientation; can cause cancer with long‐term exposure | \n
\n | \n | Naphthalene | \nReactive toxic | \nCan damage liver; prolonged vapor exposure has led to cataract formation | \n
27. Antibacterial cleaner | \nV | \nAmmonia, detergents, lye | \nToxic | \nFumes can irritate eyes and lungs; can cause burns or rashes on skin; can produce deadly chloramine gas if mixed with chlorine‐containing products | \n
\n | \n | Cresol | \nCorrosive | \nCan be corrosive to tissue; damages liver, kidneys, lungs, pancreas and spleen | \n
\n | \n | Phenol | \nCorrosive | \nCan cause central nervous system depression; severely affect circulatory system; corrosive to skin; suspected of causing cancer | \n
\n | \n | Pine oil | \n\n | Can irritate eyes and lining of nose, mouth, and throat | \n
28. Hair dyes | \nIII | \nPigment ammonia | \nToxic | \nCan cause burns or rashes on skin; can produce deadly chloramine gas if mixed with chlorine‐containing products | \n
29. Skin creams | \nIII | \nHeavy metals | \nToxic | \nCan cause nerve and kidney damage; is thought to cause cancer | \n
30. Glue | \nVI | \nXylene, toluene | \nFlammable toxic | \nIrritation of eyes, mucous membrane, and skin; effects reproductive system; probable human carcinogen of medium carcinogenic hazard | \n
To test the level of awareness and management of HHWs in sub‐Saharan Africa, 50 questionnaires were administered to students at various levels of study in tertiary institutions in Kenya, Nigeria, and South Africa. The collected data were analyzed using Microsoft Excel 2013 version and the results were presented in bar charts.
\nThe management of hazardous wastes remains a central environmental issue internationally [2]. Otoniel et al. [27] reported that measures have been taken for the HHW management in some developed countries such as the USA. In developing countries, many of which are in sub‐Saharan Africa, there is little information concerning the management of HHWs. Although there is a great challenge to the effective treatment and disposal of HHWs in most developing countries of the world, huge success has been recorded in some developed countries (such as the USA, Austria, Germany, Italy, Denmark, the Netherlands, and some other European nations) of the world. The key to this success involves creating adequate awareness on the potential health and environmental risk of HHWs through various informational campaigns [4]. Some of the developed countries have recycling and collection sites where citizens can drop HHWs at no cost. In other cases, there are collection centers such as shops take back or containers parked at public places where individuals can drop HHWs [4]. The success of this method depends largely on active participation from the public. Apart from this system, some countries also incorporate the collection of HHWs in special containers alongside with general municipal wastes, or sometimes by other special arrangements already known to the citizens. The citizens are taught to separate these wastes at the household level [4].
\nDue to the complexity of HHWs, they are not often collected as a composite waste from households. They are usually separated into different forms such as used and expired batteries, used oil, pesticides, low energy light bulbs and fluorescent tubes, pharmaceuticals, e‐waste, fertilizers, and paints. Most recyclable HHWs such as batteries and florescent lamps are recycled and reused, while others that require further treatment are sent to chemical‐physical treatment plants, thermal treatment and recovery plants, specialized treatment and recycling plants, biomechanical pretreatment plants for residual waste, sorting plants for separately collected waste, and internal thermal treatment plants [4]. There are also adequate policies and legislation on the use of HHWs in most of these countries. Otoniel et al. [27] reported that measures have been taken for the HHWs management in some developed countries but this is not true for many other developed and almost all developing countries of the world.
\nIn developing countries, many of which are in sub‐Saharan Africa, there is little information concerning the management of HHWs. Generally, solid waste management which is simpler compared to the management of HHWs in sub‐Saharan African does not meet international collection, recycling, and disposal guidelines. Most wastes generated including HHWs are disposed along roads, highways, vacant land, river banks, and canals, and among others (Figure 1). A few cities in sub-Saharan Africa (such as Cape Town in South Africa and Mbabane in Swaziland) have a well-planned solid waste collection system comparable to that of developed countries; while majority of cities (e.g. Onitsha in Nigeria and Kumasi in Ghana) have poor solid waste collection and disposal management. Many villages in the region do not have any form of waste collection and disposal system (Figure 1).
\nRecently, some contaminants, known as emerging contaminants, have been detected in drinking water of most places in the world. Notable emerging contaminants include: pharmaceuticals and personal care products (PPCPs), flame retardants, endocrine disrupting compounds (EDCs), pesticides, hormones, and disinfection by‐products (DBPs) [28]. Most of these contaminants have been linked to the use and improper disposal of HHWs. They are currently receiving global attention due to the perceived threat they could pose to public health and the environment.
\nIn most sub‐Saharan countries, the common methods for HHWs management and treatment include open burning of wastes, incineration, and landfilling. These methods are preferred over other methods because they are cheap, easy to operate, and generally accessible. As stated earlier, HHWs in domestic wastes are not separated from the nonhazardous components and are treated as a composite waste.
\n1. Open burning technique which include all forms of controlled and uncontrolled waste combustion practices is used in for the treatment of HHWs [29, 30]. This method is often used because it is cheap and easy to operate and its energy requirement is low. It does not require any formal training to burn hazardous materials. A major disadvantage to this method is the formation of harmful products such as polycyclic aromatic hydrocarbons that are easily formed from the combustion reaction of carbonaceous materials with free oxygen in air [5]. The combustion of chlorine‐containing substances can lead to the formation of dioxins and furans that are highly carcinogenic to humans [9]. Also, smoke and unpleasant odors often accompany open burning practices which is a threat to public health (Figure 2) [31]. The use of open burning techniques of HHWs has been reported in Nigeria, Cameroon, Ghana, Kenya, Tanzania, South Africa, and other countries in sub‐Saharan Africa [29–34].
\nOpen burning of some HHWs [31].
2. Incineration technique is a very useful method for the treatment of HHWs globally. It is one of the methods still in use in different developed countries of the world [4]. Incineration of HHWs should be done in a controlled environment where the release of toxic substances is eliminated [4]. This is not true for most developing countries as incineration is usually done in an uncontrolled environment [29]. This technique is very useful for the treatment of wastes with low‐water content but its application is inefficient in treating wastes containing high quantity of water; hence, it is not suitable in developing countries [34]. The release of toxic metals such as mercury, cadmium, and lead into the environment has been linked to the incineration of HHWs under the uncontrolled environment.
\n3. Landfilling is not accepted as an efficient way of treating HHWs in most developed countries due to various health and environmental risks associated with it. However, in most developing countries, HHWs end up in landfill sites as mixed waste with other domestic and medical wastes. This practice has been reported to have several environmental consequences including contamination of groundwater resource, injury of waste workers, and risks to local waste collectors who collect some discarded materials for recycling [5]. Landfilling of hazardous wastes has been reported to be unsuitable due to the complexity and nature of the wastes [2, 5, 9]. Fauziah and Agamuthu [35] reported a mixture of HHWs and nonhazardous wastes in a municipal landfill in Malaysia, of which about 1.5% of household wastes were classified as hazardous waste. Such a system of disposal is very dangerous to scavengers of valuable and recyclable wastes as they are faced with all forms of risk going through a pile of solid wastes. Cases of HHWs in landfills of developed countries have been reported despite several measures that have been setup [36].
\nApart from the general methods discussed above, several countries in sub‐Saharan have devised other initiatives for the management of certain classes of HHWs. In South Africa, a private company that makes rechargeable batteries organized with a well‐known food stores nationwide to collect all types of batteries. The recyclable batteries are sorted from the nonrecyclable batteries and are sent to France for recycling because there are no facilities in South Africa that can recycle batteries. The nonrecyclable batteries are encapsulated in concrete and disposed of safely to a licensed landfill [37]. Similarly, a nonprofit organization known as Recycling Oil Saves the Environment receives used oil from various locations in South Africa and recycles them for use [38]. In Maldives, Bluepeace [39] reported the use of a ditch (Figure 3) at the waste collection center for the disposal of used engine oil. This consequently led to groundwater contamination.
\nUsed engine oil in a ditch in Male, Maldives contaminates the groundwater [34].
Other methods reported for the treatment of HHWs include using them as a fuel in cement kilns, as components of building materials (roads, bricks etc.), and autoclaving and electrothermal deactivation. These methods are used in some sub‐Saharan Africa countries but the unintended consequences of these technologies are still not known [37].
\nSeveral factors that usually interfere with the management of HHWs in sub‐Saharan Africa include:
\n1. Lack of awareness: One of the major factors affecting HHW management is lack of awareness of what household hazardous wastes are. The limited information on the management of HHW in sub‐Saharan Africa attests to the fact that very little is known about them in the region. Most people in sub‐Saharan Africa hardly read the labels on the product they purchase to follow the disposal procedure. Even those that read the labels ignore the disposal instructions from the manufacturers of those products. This is because there is limited understanding of the possible risk HHWs have on humans and the environment. Children play with flammable substances at home or after improper disposal. One of the greatest successes that can be recorded in HHW management is the separation of these substances from other wastes at the household level.
\nFrom the results obtained from the questionnaires administered, the participants were majorly undergraduate and postgraduate students within the age group of 15–40 years. The participants were males comprising 58, 88, and 40%from South Africa, Nigeria, and Kenya, respectively (Figure 4).
\nGender distribution of participants.
In South Africa, 68% of the participants claimed to have adequate knowledge of household hazardous wastes, while 32% of the participants did not know (Figure 5). In the classification on the types of HHWs, various types of HHWs were included in the questionnaire as a follow‐up question to help in estimating those who truly have adequate knowledge of HHWs. Based on this classification, 43% (out of this 68%) of the participants actually knew what HHWs were while 57% of the participants did not know. There was high variation in the awareness of HHWs, inferring partial awareness of HHWs among tertiary students of South Africa. In Nigeria, 69% of the participants also claimed to have adequate knowledge of HHWs while 31% lacked adequate knowledge of HHWs (Figure 5). But based on the classification on the types of HHWs, 40% (out of the 69%) of the participants actually knew what HHWs are and 60% of the participants did not know. The awareness level in Nigeria is similar to that in South Africa. In Kenya, a different scenario was obtained compared to South Africa and Nigeria. 36% of the participants claimed that they had adequate knowledge of HHWs and 64% of the participants did not know (Figure 5). From the classification of various types of HHWs, all the participants who claimed to have adequate knowledge of HHWs truly had a good level of awareness on HWWs based on the follow‐up questions. The level of awareness in Kenya seemed to be low compared to other two countries used in this study. The awareness level in each of the three countries could be as a result of literacy level of individual country [40] but this may not only be the case as the sincerity of each participant in answering the questions can be a contributing factor. Some people who claimed to have adequate knowledge of HWWs from South Africa and Nigeria actually did not adequate knowledge, as demonstrated from a follow‐up question on the classification of various substances as HHWs and nonhazardous wastes. Some of the respondents who initially claimed to have adequate knowledge on HHWs classified hazardous substances as nonhazardous.
\nPercentage level of participant\'s knowledge on HHWs.
With the exception of level of knowledge of the respondents, many participants claimed to know how to manage HHWs from their homes. In South Africa, 62% of the participants had adequate knowledge of HHWs management whereas 38% did not know (Figure 6). The participants suggested various ways of storage of HHWs which included: closed container (64%), open container (2%), plastic bag (14%), pile in yard (2%), recycling (4%), and do not know at all (14%). 74% of the participants admitted that HHWs could have many negative effects on humans and the environment; 14% suggested that they will only have mild effects; 2% agreed that HHWs would have no effect on man and the environment. In Nigeria, 48% of the respondents claimed to have adequate knowledge of HHWs management, while 52% did not know (Figure 6). 73% of the participants suggested that HHWs should be separated from other household wastes. Similarly, 71% of the participants suggested that HHWs should be stored in a closed container; 2% suggested open container; 2% plastic bags, and 25% did not know how to store HHWs. 56% of the participants admitted that HWWs could have many ill-effects on humans and the environment while 17% believed they may have mild effects and 27% were not sure of their effects. In Kenya, 32% of the participants had good knowledge of HHWs management whereas 68% did not know how to manage HHWs (Figure 6). A majority of the participants suggested that HHWs should be separated from other household wastes and that closed container was the best way to store HHWs in the household. 68% of the participants admitted that HWWs could have many ill-effects on humans and the environment while 32% claimed that they will only have mild effects.
\nPercentage of participant\'s level of knowledge on HHWs management.
The government and other private bodies such as NGOs must educate people in sub‐Saharan Africa on HHWs and their management. This can be achieved through rallies, posters, social media (such as Facebook, twitter, WhatsApp), newspapers, television, and using other respected authorities like traditional leaders (e.g., chiefs), school teachers, university lecturers, and religious leaders.
\n2. Financial constraints: Most countries in sub‐Saharan Africa are faced with unprecedented population growth which is often unbalanced with much of the disposable municipal expenditure devoted to high profile infrastructure whereas waste disposal and management are low on the list of priorities in terms of allocation of funds [41]. Poverty and unemployment are the major focus of most governments in sub‐Saharan countries. The treatment of HHWs is cost intensive and without proper allocation of funds such management systems cannot be effective. Most countries in the region have attempted to carry out solid waste management in one form or the other and have reported minimal success due to limited financial commitment from government, the people and NGOs. Most people in the region are striving to meet their basic needs and are not willing to pay an extra cost for waste disposal. Several countries in developing countries have placed a ban on certain product containing hazardous ingredient. The accumulation of such products already in the country occurs due to financial constraints and lack of appropriate technologies to treat and dispose them. Also despite the ban, illegal importation of such products is common due to poor monitoring for compliance and corruption [42].
\n3. Unplanned settlements: Very few cities and villages within the region have planned settlements; the latter make collection of HHWs easy but within most cities, slums and high rate of urbanization make it very difficult for the government or private companies to effectively distribute waste bins and collect them. Some of the places where people live are not accessible to the collection vehicles.
\n4. Lack of appropriate technology: Government officials in most countries, as stated earlier, are more concerned with poverty eradication, solving unemployment problems, and provision of basic health care and education and are unwilling to invest in the technology for the management of HHWs. Most facilities present in a few countries lack the appropriate technology from the waste collection to disposal. If progress is to be made in this regard, there is an urgent need for the appropriate technologies and skillful personnel. Agamuthu [8] and Gatke [43] reported that the main components of HHWs in Malaysian landfills are batteries, aerosol cans, paints, pesticides, adhesive, drugs, and syringes. They lamented the reason of these contaminants in the landfills as the Malaysian government did not have the appropriate technologies for the management of HHWs hence their inclusion with general domestic wastes. Similar observation has been reported in many countries in sub‐Saharan Africa.
\n5. Lack of proper legislation and enforcement of the legislation: Most countries within the region lack the legal framework for HHWs disposal; therefore efforts to control it would be unsuccessful. Most developing countries in sub‐Saharan Africa have a legislative framework for solid waste management and wastewater whereas some developed countries such as Canada, Germany, and the USA have a realistic policy on household hazardous wastes with the aim of reducing it at the household level [4, 36]. The legislative framework for both liquid and solid wastes has not been enforced, even though present. There is no accountability system in the legal structure’ thus, even when the laws exist there is no structure to ensure strict compliance. South Africa has quite a number of legislations governing waste and these include: the South African constitution Act 108 of 1996, Hazardous Substance Act 5 of 1973, Environmental Conservation Act 73 of 1989 and Minerals and Petroleum Resources Development Act 28 of 2002, National Environmental Management: Waste Act 59 of 2008, and among others but there is no legislation that strictly governs HHWs in the country [44]. In Nigeria, several legislations regarding waste management include the National Environmental Standards and Regulations Enforcement Agency Act, 2007; the Environmental Impact Assessment Act, 1992; and the Harmful Waste Act, 1988 [34, 45]. The Harmful Waste Act of 1988 in Nigeria prohibits the sale, purchase, and generation of toxic, poisonous, and potentially injurious substances [34, 45]. Similarly in Kenya, the Environmental Management and Co‐ordination Act (EMCA) No. 8 of 1999 prohibits the mismanagement of wastes and has a deterrent fine for industries that refuse to comply with the tenets of the policy. The Act also compels polluters to manage and recycle their wastes. There are several portions of the Act dealing with hazardous wastes [46]. Most countries in sub‐Saharan Africa have different legislations on solid wastes and wastewater but specific legislations on HHWs management is completely missing. Several part of the legislations and policies deal with hazardous wastes in a broader sense but HHW was not the sole target of the legislations [15–18]. This may be one of the contributing factors to the low level of awareness and management of HHWs in the region.
\nThe way forward for effective management of HHWs in sub‐Saharan Africa is to first create active awareness through information campaigns on HHWs and the health and environmental risks associated with them. The use of substances without hazardous components should be encouraged as this will lead to a reduction of total HHWs generated in sub-Saharan Africa. Collection, recycling and treatment centers should be opened by the government where hazardous wastes can be disposed without any financial cost on the citizens. Different types of HHWs such as batteries, engine oil, paints, and light bulbs should be collected separately and recycled for reuse. The government should make HHWs management a priority and should invest in it. Also, the government through the various ministries should seek for funding through the writing of good proposals soliciting for grants from donors to assist in the management of HHWs. Adequate technologies for HHWs treatment should be introduced and where there are no skilled personnel, scholarship should be given to interested individuals to study HHWs treatment and management from countries such as France and Austria where HHWs management have been successfully implemented for decades. Such individuals should be encouraged to return back to their respective countries to implement what they have learnt. Adequate policy and legislation on HHWs should be enacted and enforced through proper monitoring for compliance.
\nHHWs have high potential risks. In order to avoid this, it is desirable that strict monitoring be given to the use, storage, and disposal of hazardous substances at the household level. Improper handling and disposal of these materials can be detrimental to human health and the environment at large. Results from this study have shown low level of awareness of HWWs among university students who are expected to be more enlightened than those who did not have the privilege to acquire tertiary education. Therefore, more ignorance on HHWs is expected from other citizens of the region because if university students could not identify what HHW substances are and do not understand the potential risk they pose to public health and the environment, then other less‐educated people are not likely to have enough information on HHWs. Major steps to the efficient management of HHWs includes creating adequate awareness on3 HHWs, encouraging citizens to use alternative substances in lieu of them. People in the region should be enlightened on the use, disposal and the potential risk associated with HHWs. There should be adequate policies on HHWs management and the enforcement of such policies in sub‐Saharan Africa. Little information and data exists on HHWs in sub-Saharan Africa, more studies should be encouraged and conducted to assess their levels.
\nThe authors are grateful to Salome Delaila Achieng who helped in distributing the questionnaires to students in Kenya. The effort of Elizabeth T. Rogawski in proof reading the draft form of the manuscript is highly appreciated.
The secondary metabolism is a biosynthetic source of several interesting compounds useful to chemical, food, agronomic, cosmetics, and pharmaceutical industries. The secondary pathways are not necessary for the survival of individual cells but benefit the plant as a whole [1]. Another general characteristic of secondary metabolism is that found in a specific organism, or groups of organisms, and is an expression of the individuality of species [2]. The secondary metabolism provides chemical diversity to organic molecules with low molecular weight that are related by the respective pathways; such organic molecules are called secondary metabolites. The secondary metabolites are often less than 1% of the total carbon in plant molecules [3]. These organic molecules isolated from terrestrial plants are the most studied, and their syntheses have an important role in the protection against pathogens, unfavorable temperature and pH, saline stress, heavy metal stress, and UVB and UVA radiation [3]. Secondary metabolism reflects plant environments more closely than primary metabolism [4]. There are three principal kinds of secondary metabolites biosynthesized by plants: phenolic compounds, terpenoids/isoprenoids, and alkaloids and glucosinolates (nitrogen- or sulfur-containing molecules, respectively) [5]. Phenolic compounds are biosynthesized by the shikimate pathway and are abundant in plants. The shikimate pathway, in plants, is localized in the chloroplast. These aromatic molecules have important roles, as pigments, antioxidants, signaling agents, electron transport, communication, the structural element lignan, and as a defense mechanism [6], Figure 1. The seven steps of the shikimate pathway and the metabolites for branch point are described in this chapter, as factors that induce the synthesis of phenolic compounds in plants. Some representative examples that show the effect of biotic and abiotic stress on the production of phenolic compounds in plants are discussed.
\nPhenolic compound biosynthesis promoted by biotic and abiotic stresses (e.g., herbivores, pathogens, unfavorable temperature and pH, saline stress, CO2, O3, heavy metal stress, and UVB and UVA radiation).
The shikimate biosynthesis pathway provides precursors for aromatic molecules in bacteria, fungi, apicomplexan, and plants, but not in animals [2, 7]. Shikimic acid is named after the highly toxic Japanese shikimi (Illicium anisatum) flower from which it was first isolated [8]. This biochemical pathway is a major link between primary and secondary metabolism in higher plants [6]. In microorganisms, the shikimate pathway produces aromatic amino acids L-phenylalanine (L-Phe), L-tyrosine (L-Tyr), and L-tryptophan (L-Trp), molecular building blocks for protein biosynthesis [9]. But in plants, these aromatic amino acids are not only crucial components of protein biosynthesis; they also serve as precursors for diverse secondary metabolites that are important for plant growth [10]. These secondary metabolites are called phenolic compounds and are synthesized when needed by the plant [11]. These molecules play an important role in the adaptation of plants to their ecosystem, and their study advances biochemical techniques and molecular biology [3, Bourgaud]. The principal aromatic phenolic compounds synthesized from L-Phe and L-Tyr are cinnamic acids and esters, coumarins, phenylpropenes, chromones (C6-C3), stilbenes, anthraquinones (C6-C2-C6), chalcones, flavonoids, isoflavonoids, neoflavonoids (C6-C3-C6), and their dimers and trimers, respectively (C6-C3-C6)2,3, lignans, neolignans (C6-C3)2, lignans (C6-C3)n, aromatic polyketides, or diphenylheptanoids (C6-C7-C6) [12]. L-Trp is a precursor of alkaloids in the secondary metabolism [2]. Additionally, diverse hydroxybenzoic acids and aromatic aldehydes (C6-C1) are biosynthesized via branch points in the shikimate pathway, Figure 2. Phenolic compounds biosynthesized from the shikimate pathway have structural versatility.
\nThe shikimic and chorismic acids are the common precursors for the synthesis of L-Phe, L-Tyr, and L-Trp and diverse phenolic compounds.
The shikimate pathway consists of seven sequential enzymatic steps and begins with an aldol-type condensation of two phosphorylated active compounds, the phosphoenolpyruvic acid (PEP), from the glycolytic pathway, and the carbohydrate D-erythrose-4-phosphate, from the pentose phosphate cycle, to give 3-deoxy-D-arabino-heptulosonic acid 7-phosphate (DAHP), Figure 3. The seven enzymes that catalyze the pathway are known: 3-deoxy-D-arabino-heptulosonate-7-phosphate synthase (DAHPS; EC 4.1.2.15, now EC 2.5.1.54), 3-dehydroquinate synthase (DHQS; EC 4.2.3.4), 3-dehydroquinate dehydratase/shikimate dehydrogenase (DHQ/SDH; EC 4.2.1.10/EC 1.1.1.25), shikimate kinase (SK; EC 2.7.1.71), 5-enolpyruvylshikimate 3-phosphate synthase (EPSPS; EC 2.5.1.19), and chorismate synthase (CS; EC 4.2.3.5) [13], Table 1.
\nShikimate pathway.
Reaction step | \nSubstrate | \nEnzyme/cofactor | \nProduct | \n
---|---|---|---|
1 | \nPhosphoenolpyruvate (PEP), erythrose-4-phosphate | \n3-Deoxy-D-arabino-heptulosonate-7-phosphate synthase (DAHPS; EC 4.1.2.15, now EC 2.5.1.54)/Co2+, Mg2+ or Mn2+ [15] | \n3-Deoxy-D-arabino-heptulosonic acid 7-phosphate (DAHP), Pi | \n
2 | \n3-Deoxy-D-arabino-heptulosonic acid 7-phosphate (DAHP) | \n3-Dehydroquinate synthase DHQS (EC. 4.2.3.4)/Co2+, NAD+ [15, 16] | \n3-Dehydroquinic acid (DHQ), Pi | \n
3 | \n3-Dehydroquinic acid (DHQ) | \n3-Dehydroquinate dehydratase (DHQ dehydratase EC 4.2.1.10) [15] | \n3-Dehydroshikimic acid (DHS), H2O | \n
4 | \n3-Dehydroshikimic acid (DHS), NADPH + H+ | \nShikimate dehydrogenase (SDH; EC 1.1.1.25) [18, 19, 20, 21] | \nShikimic acid, NADP+ | \n
5 | \nShikimic acid, ATP | \nShikimate kinase enzyme (SK; EC 2.7.1.71) | \nShikimic acid 3-phosphate (S3P), ADP | \n
6 | \nShikimic acid 3-phosphate (S3P), PEP | \n5-Enolpyruvylshikimate 3-phosphate synthase, also called aroA enzyme (EPSPS; EC 2.5.1.19) [25] | \n5-Enolpyruvylshikimate 3-phosphate (EPSP), Pi | \n
7 | \n5-Enolpyruvylshikimate 3-phosphate (EPSP) | \nChorismate synthase (CS; EC 4.2.3.5)/FMNH2 [2, 19, 30, 31] | \nChorismic acid, Pi | \n
Substrates, enzymes, and products of the shikimate pathway.
Pi, phosphate; NAD+, oxidized nicotinamide adenine dinucleotide; NADPH, reduced nicotinamide adenine dinucleotide phosphate; FMNH2, reduced flavin mononucleotide.
The shikimate pathway has special characteristics that are present only in bacteria, fungi, and plants. The absence of the pathway in all other organisms provides the enzymes catalyzing these reactions with potentially useful targets for the development of antibacterial agents and herbicides. For example, 5-enolpyruvylshikimate 3-phosphate synthase (EPSP-synthase) catalyzes the transfer of the enolpyruvyl (carboxyvinyl) moiety from PEP to shikimic acid 3-phosphate (S3P) [6].
\nIn the second reaction step, DAHP loses phosphate (Pi); the enolic-type product is cyclized through a second aldol-type reaction to produce 3-dehydroquinic acid (DHQ). The 3-dehydroquinate synthase (DHQS) catalyzes this cyclization in the shikimate pathway. The DHQ dehydrates to produce 3-dehydroshikimic acid (DHS) (3-dehydroquinate dehydratase); this compound has a conjugated double carbon-carbon, Figure 3. The protocatechuic and the gallic acids (C6-C1) are produced by branch-point reactions from DHS [2]. The fourth step in the pathway is a reduction reaction of DHS with reduced nicotinamide adenine dinucleotide phosphate (NADPH), Figure 3. The fifth section of the pathway is the activation of shikimic acid with adenosine triphosphate (ATP) (shikimate kinase, SK) to make shikimic acid 3-phosphate (S3P). The sixth chemical reaction is the addition of PEP to S3P to generate 5-enolpyruvylshikimic acid 3-phosphate; the enzyme that catalyzes this reaction step, 5-enolpyruvylshikimate 3-phosphate synthase (EPSPS), has been extensively studied. The reason for this interest is because glyphosate [N-(phosphonomethyl)glycine] is a powerful inhibitor of EPSPS [2], so glyphosate has been used as a broad-spectrum systemic herbicide. It is an organophosphorus molecule, phosphonic acid, and glycine derivative that has a similar molecular structure to PEP, Figure 4.
\nPEP and glyphosate (powerful inhibitor of the 5-enolpyruvylshikimate 3-phosphate synthase, EPSPS).
The last reaction step of the shikimate pathway is the production of chorismic acid from catalytic action on the chorismate synthase (CS). This reaction is a 1,4-trans elimination of Pi, to yield the conjugated molecule, chorismic acid, Figure 3.
\nThe first reaction of the shikimate pathway is an aldol-type condensation of PEP and carbohydrate erythrose-4-P, to give 3-deoxy-D-arabino-heptulosonic acid 7-phosphate (DAHP), Figures 3 and 5. A new stereogenic center is generated in the condensation product DAHP catalyzed by the 3-deoxy-D-arabino-heptulosonate-7-phosphate synthase enzyme (DAHPS; EC 4.1.2.15, now EC 2.5.1.54). Results of enzymatic kinetic and labeled PEP with tritium (Z)-[3-3H] PEP suggest that the nucleophilic attack of PEP is from the Si face of PEP to the Re face of the carbonyl group of D-erythrose-4-P, Figure 5 [14]. Two isoenzymes of DAHPS have been found for the catalysis of this first reaction step. One isozyme needs only Mn2+, and the other, either Co2+, Mg2+, or Mn2+ for the catalysis [15].
\nStereochemistry of the condensation reaction of (Z)-[3-3H]PEP and D-erythrose-4-phosphate by DAHP synthase [14].
The second reaction of the shikimate pathway is an intramolecular aldol-type reaction cyclization, where the enol (C6-C7) of DAHP nucleophilically attacks the carbonyl group (C2), to produce a six-member cycle, the 3-dehydroquinic acid (DHQ), Figures 3 and 6. The enzyme that catalyzes this reaction, 3-dehydroquinate synthase DHQS (EC. 4.2.3.4), is a carbon-oxygen lyase enzyme that requires Co2+ and bound oxidized nicotinamide adenine dinucleotide (NAD+) as cofactors [15, 16]. The Co2+ is essential for the catalytic activity of DHQS. Bender et al. [16] found that DHQS, from Escherichia coli, is a monomeric metalloenzyme that contains tightly bound Co2+, and DHQS is deactivated with ethylenediaminetetraacetic acid (EDTA). The presence of the substrate (DAHP) blocks the inactivation by EDTA. The NAD+ cofactor dissociates form the DHQS enzyme rapidly in the presence of DAHP [16]. The reaction mechanism of the enzyme-catalyzed conversion of DAHP to DHQ involves five transformations from the DAHP hemiketal form, a pyranose: (1) oxidation of the hydroxyl at C5 adjacent to the lost proton that requires NAD+ (NAD+ need never dissociate from the active site), (2) the elimination of Pi of C7 to make the α,β-unsaturated ketone, (3) the reduction of C5 with NADH + H+, (4) the ring opening of the enol to yield an enolate, and (5) the intramolecular aldol-like reaction to produce DHQ. All five-reaction steps occur through the function of DHQS, Figure 6.
\nReaction mechanism of DAHP (hemiketal form) to 3-dehydroquinic acid (DHQ) by 3-dehydroquinate synthase DHQS (EC. 4.2.3.4) [16].
The reduction reaction of DHQ leads to quinic acid at this branch point in the shikimate pathway. Quinic acid is a secondary metabolite that is free, forming esters or as part of alkaloids such as quinine. Quinic acid is found in high quantities in mature kiwi fruit (Actinidia chinensis and other species of Actinidia) and is a distinguishing characteristic of fresh kiwi fruit [7]. Also, the quinic acid is abundant in roasted coffee [17].
\nThe third and fourth reaction steps of the shikimate pathway are catalyzed by a bifunctional enzyme: 3-dehydroquinate dehydratase/shikimate dehydrogenase (DHQ dehydratase/SDH; EC 4.2.1.10/EC 1.1.1.25). The DHQ dehydratase enzyme is a hydro-lyase kind, and the SDH is an oxidoreductase enzyme. The DHQ dehydratase, in the third reaction step, converts DHQ into 3-dehydroshikimic acid (DHS) by eliminating water, and this reaction is reversible, Figure 7. The DHS is converted to shikimic acid in the fourth reaction step, by the reduction of the carbonyl group at C-5 by the catalytic action of SDH with NADPH, Figure 3. The biosynthesis of DHS is a branch point to shikimic acid and to the catabolic quinate pathway. If the DHS dehydrates, it produces protocatechuic acid (C6-C1) or gallic acid, Figure 3. Gallic acid (C6-C1) is a hydroxybenzoic acid that is a component of tannins [2].
\nReaction mechanism to produce 3-dehydroshikimic acid (DHS) by type I DHQ dehydratase enzyme [21].
Two structurally different kinds of 3-dehydroquinate dehydratase are known: type I (not heat-stable) and type II (heat-stable). Type I enzyme is present in bacteria and higher plants, and type II is found in fungi, which have both types of enzymes [18, 19]. The catalytic mechanism of the type I DHQ dehydratase has been detected by electrospray MS [20]. This catalytic mechanism involves the amino acid residue Lys-241 that forms a Schiff base with the substrate and product, Figure 7 [21]. The fourth step is the reduction of DHS with NADPH that enantioselectively reduces the carbonyl of the ketone group of DHS to produce shikimic acid (shikimate dehydrogenase, SDH), Figure 3.
\nSigh and Christendat [22] reported the crystal structure of DHQ dehydratase/SDH from the plant genus Arabidopsis. The crystal structure has the shikimate bound at the SDH and the tartrate molecule at the DHQ dehydratase. The studies show that Asp 423 and Lys 385 are key catalytic amino acids and Ser 336 is a key-binding group.
\nThe shikimate kinase enzyme (SK; EC 2.7.1.71) catalyzes the phosphorylation of the shikimic acid, the fifth chemical reaction of the shikimate pathway, and the products are shikimic acid 3-phosphate (S3P) and ADP, Figures 3 and 8. Shikimic acid is phosphorylated with ATP in the 5-hydroxyl group of shikimic acid. SK is an essential enzyme in several bacterial pathogens and is not present in the human cell; therefore the SK enzyme has been classified as a protein target for drug design, especially for chemotherapeutic development of antitubercular drugs [23, 24].
\nPhosphorylation of shikimic acid with ATP.
The 5-enolpyruvylshikimate 3-phosphate synthase, also called aroA enzyme (EPSPS; EC 2.5.1.19), catalyzes the condensation of PEP to the 5-hydroxyl group of S3P in the sixth reaction of the shikimate pathway to form 5-enolpyruvylshikimate 3-phosphate (EPSP). The reaction mechanism involves the protonation of PEP to subsequent nucleophilic attack of the hydroxyl at C-5 of S3P to form an intermediate that loses Pi to form EPSP, Figure 9 [25].
\nReaction mechanism of the condensation of S3P with PEP by EPSPS (EC 2.5.1.19) to form EPSP [25].
EPSPS is the most studied enzyme of the shikimate pathway because it plays a crucial role in the penultimate step. If this enzyme is inhibited, there is an accumulation of shikimic acid [26], and the synthesis of aromatic amino acid is disabled, leading to the death of the plant [27]. Therefore, EPSPS is used as a target for pesticides, like glyphosate, Figure 4, the active ingredient in the herbicides RoundUp™, Monsanto Chemical Co., and Touchdown™, Syngenta. Glyphosate (N-(phosphonomethyl)glycine) inhibits EPSPS and is a potent nonselective herbicide that mimics the carbocation of PEP and binds EPEPS competitively [28]. Because the glyphosate is nonselective and kills food crops, there is interest in finding glyphosate-tolerant genes for genetically modified crops [29]. Two types of EPSPS enzymes have been identified: type I EPSPS (sensitive to glyphosate) identified mostly in plants and bacteria and type II EPSPS (nonsensitive to glyphosate and has a high affinity for PEP), found in some bacteria [27].
\nThe seventh and last reaction step of the shikimate pathway is the 1,4-trans elimination of the Pi group at C-3 from EPSPS to synthetize chorismic acid. This last step is catalyzed by chorismate synthase (CS; EC 4.2.3.5) that needs reduced flavin mononucleotide (FMNH2) as a cofactor that is not consumed [2, 19]. The FMNH2 transfers an electron to the substrate reversibly [30]. Spectroscopic techniques and kinetic isotope effect studies suggest that a radical intermediate in a non-concerted mechanism is developed [30, 31], Figure 10. Chorismic acid, the final molecule of the shikimate pathway, is a key branch point to post-chorismic acid pathways, to obtain L-Phe, L-Tyr, and L-Trp, Figure 2. L-Phe is the substrate to phenylpropanoid and flavonoid pathways [13].
\nReaction of mechanism to yield chorismic acid by chorismate synthase [30].
The expression of phenolic compounds is promoted by biotic and abiotic stresses (e.g., herbivores, pathogens, unfavorable temperature and pH, saline stress, heavy metal stress, and UVB and UVA radiation). UV radiation is divided into UVC (≤280 nm), UVB (280–320 nm), and UVA (300–400 nm). UVA and UVB radiation are transmitted through the atmosphere; all UVC and some UVB radiation (highly energetic) are absorbed by the Earth’s ozone layer. This accumulation is explained by the increase in enzymatic activity of the phenylalanine ammonia-lyase and chalcone synthase enzymes, among others [12]. Studies have been done about the increase of phenolic compounds, such as anthocyanins, in plants when they are exposed to UVB radiation [13]. Another study demonstrates that UVB exposure enhances anthocyanin biosynthesis in “Cripps pink” apples (Malus x domestica Borkh.) but not in “Forelle” pears (Pyrus communis L.) [32]. This effect may be due to UV radiation exposure and the cultivar of the plants studied. It is known that if plants are under stress, they accumulate phenolic compounds.
\nThe increase in phenolic compounds in blueberry (Vaccinium corymbosum) plantlets cultivated in vitro exposed to aluminum (Al) and cadmium (Cd) has also been studied. These heavy metals cause high toxicity in plants, because they increase the oxidative stress by the production of reactive oxygen species (ROS). The authors of the study suggest that the phenolic compounds, specifically chlorogenic and ellagic acids, Figure 11, reduce the ROS in blueberry plants [33].
\nChemical structure of chlorogenic (C6-C3) and ellagic (C6-C1) acids.
An interesting study was carried out in 2011 by Mody et al., where they studied the effect of the resistance response of apple tree seedlings (Malus x domestica) to a leaf-chewing insect (Spodoptera littoralis) [34]. The authors found a significant herbivore preference for undamaged plants (induced resistance) was first observed 3 days after herbivore damage in the most apical leaf. Also, the results showed higher concentrations of the flavonoid phlorizin, Figure 12, in damaged plants than undamaged plants. This indicates that insect preference for undamaged apple plants may be linked to phlorizin, which is the main secondary metabolite of the phenolic type in apple leaves.
\nChemical structure of phlorizin (C6-C3).
Knowledge of the biosynthetic pathway of shikimic acid leads to understanding the reaction mechanisms of enzymes and thus discovering antimicrobials, pesticides, and antifungals. Studies with isotopic labeling of substrates, the use of X-ray diffraction, nuclear magnetic resonance (NMR), mass spectrometry (ES), biotechnology, as well as organic synthesis have contributed to explaining the shikimate pathway. Although the seven steps of the biosynthetic pathway are elucidated, these metabolites are the precursors of phenolic compounds, more complex molecules that are necessary for the adaptation of plants to the environment. So, the shikimate pathway is the basis for the subsequent biosynthesis of phenolic compounds. There is scientific interest in continuing to investigate the biosynthesis of phenolic compounds from several points of view: pharmaceuticals, agronomy, chemical and food industries, genetics, and health.
\nThe authors thank Carol Ann Hayenga for her English assistance in the preparation of this manuscript. The Technological University of the Mixteca provided support.
\nThe authors have no conflict of interest to declare and are responsible for the content and writing of the manuscript.
This chapter does not contain any studies with human participants or animals performed by any of the authors.
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