FACULTY OF APPLIED SCIENCESB. Sc. (Hons.) ENVIRONMENTAL TECHNOLOGY
EVT 577 : WASTEWATER TECHNOLOGY
ASSIGMENT NO : 1
TITLE : THE CASE STUDY REPORT ON WASTEWATER FROM PESTICIDE INDUSTRY
GROUP : AS2294A
GRADER : NURUL NADIAH MOHD FIRDAUS
DATE OF EXPERIMENT
: 29 MARCH 2016
NAME / STUDENT ID : 1) MOHD FAHMI BIN MOHD YUSOF 2014415098
1TABLE OF CONTENT
Content Pages
Abstract
Component Of Wastewater
Management and Technology Involved1. The Determination of Organonitrogen Pesticides in Municipal
and Industrial Wastewater(USA)2. The Determination of Organo phosphorus Pesticides in
Municipal and Industrial Wastewater(USA)3. Wastewater Analysis By Gas Chromatoghraphy/Mass
Spectrometry (USA)4. Biological Treatment of Industrial Wastewater Using
Biosimulator (Pakistan)5. Treatment of agrochemical/Pesticide Wastewater by
Coagulation/Flocculation Process(USA)6. Combined Solar advanced oxidation and PAC adsorption for
removal of pesticides from industrial wastewater(Japan)7. Removal of pesticides from wastewater by electrochemical
methods A comparative approach(India)8. Use of Fenton's Reagent for Removal of Pesticides from
Industrial Wastewater (Poland)9. Treatment of Pesticides Industry Wastewater by Water
Hyacinth (Eichornia crassipes) (Ethiopia)
References
Appendices
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ABSTRACT
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Pesticides provide the primary means for controlling organisms that compete with man for food and fibre or cause in- jury to man, livestock and crops. They played a vital role in the economic production of wide ranges of vegetable, fruit, cereal, forage, fibre and oil crops which now constitute a large part of successful agricultural industry in many countries. After application to the target areas, pesticide residues are removed from applicators by rinsing with water which results in the formation of a toxic wastewater that represents a disposal problem for many farmers. Pesticides can adversely affect people, pets, livestock and wildlife in addition to the pests they are intended to destroy.
The phenomenon of bio- magnification of some pesticides has resulted in reproductive failure of some fish species and egg shell thinning of birds such as peregrine falcons, sparrow hawk and eagle owls. Pesticide toxicity to humans include skin and eye irritation and skin cancer. Therefore, care must be exercised in the application, disposal and treatment of pesticides. Currently, dis- posal of pesticide wastewater is carried out by: 1) land cultivation, 2) dumping in soil pits, plastic pits and concrete pits or on land and in extreme cases in streams near the rinsing operation, 3) use of evaporation beds and 4) land filling. These methods of disposal are unsafe as the surface run off will reach streams, rivers and lakes and the infiltration of the wastewater into the local soil will eventually reach ground water.
The treatment methods currently used for pesti- cide wastewater include: 1) incineration (incinerators and open burning), 2) chemical treatments (O3/UV, hydrolysis, Fenton oxidation and KPEG), 3) physical treatments (inorganic, organic absorbents and activated carbon) and 4) bio- logical treatments (composting, bioaugmentation and phytoremediation). Therefore, the choice of safe, on farm disposal techniques for agricultural pesticides is very important. A comparative analysis was performed on 18 methods of pesti- cide disposal/treatment using six criteria: containment, detoxification ability, cost, time, suitability for on farm use, size and evaporation efficiency. The results indicated that of the 18 methods evaluated, 9 scored above 80/100 and can be used on farm. They were organic absorbents (97), composting (94), bioaugmentation (92), inorganic absorbents (90), Fenton oxidation (86), O3/UV (83), activated carbon (82), hydrolysis (82), and land cultivation (80).
The other methods are not suitable for on farm use as they suffered from containment problems, high cost and variability of effectiveness. The persistent pesticides occur in the water cause potential adverse effects on the environment and public health. Due to high use of pesticides in the agricultural developed area/ country and public health sector, hence is posing a challenge to remove the pesticides from wastewater. In this paper a review of pesticides in wastewater in India is presented. The current scenario of pesticide wastewater and its various treatment methods are cited. Each method has its own advantages and limitations in terms of removing the pollutants, efficiency and economical effectiveness. Currently, membrane distillation is an effective technique can be used to treat pesticide wastewater.
Pesticide Industry
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COMPONENT OF WASTEWATER
Wastewater discharge and its management
Definition of Wastewater
Wastewater is water used and discharged from homes, commercial establishments,industries, pollution control devices, and farms. The term wastewater is now morecommonly used than sewage, although, for the most part, the terms are synonymous.Domestic or sanitary wastewater refers to waters used during the course of residentiallife or those discharged from restrooms. Industrial wastewaters refer to those generatedby an industry. Municipal wastewaters are waters used by a municipality, so they wouldusually include both sanitary and industrial wastewaters. Combined wastewater refers toa mixture of sanitary or municipal wastewaters and storm waters created by rainfall.
Industrial and Municipal Wastewater
Municipal and Industrial Wastewater Discharge
Figure 1 shows the wastewater discharge between 1991 and 2003. It can beseen that the total wastewater discharge from monitored sources almost kept stablebetween 1991 and 1998, some increase after 1998, but the trends were not consistent forindustrial and domestic wastewaters. Industrial wastewater discharges appear to havefallen slightly from 1995 to 1998 and kept almost stable after 1998, though the data donot capture unmonitored townships and village enterprises and industries. Despitelimited data, small-scale township and village enterprises and industries are known to besignificant contributors to water pollution problems in adjacent surface waters andgroundwater. Domestic wastewater discharge amounts show a growing trend. Itexceeded the amount from industrial sources in 1998. Discharges from householdswithout sewerage are not included and presumably increased by similar amounts during the same period.
Figure 1. Wastewater discharge between 1991 and 2003
A pesticide is any substance or mixture of substances used to destroy, suppress or alter the life cycle of any pest. A pesticide can be a naturally derived or synthetically produced substance. A pesticide can also be an organism, for example, the bacterium Bacillus
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thuringiensis which is used to control a number of insect pests, or even a genetically modified crop.
Pesticides include bactericides, baits, fungicides, herbicides, insecticides, lures, rodenticides and repellents. They are used in commercial, domestic, urban and rural environments.
What are some of the different types of pesticides?
Some families or groups of chemical products which are considered pesticides under current legislation are:
Bactericides -shy; These destroy, suppress or prevent the spread of bacteria. Examples are swimming pool chemicals containing chlorine, and products used to control black spot (bacterial blight) on garden plants or in orchards. Household disinfectants and some industrial disinfectants are excluded and not considered pesticides.
Baits -shy; These may be 'ready to use' products or products which need to be mixed with a food to control a pest. This category includes baits prepared for the control of large animals, such as foxes, wild dogs and rabbits, and baits for insects (such as cockroaches and ants) and molluscs (snail and slug pellets).
Fungicides -shy; These control, destroy, make harmless or regulate the effect of a fungus. Examples include chemicals used to treat Grey mould on grape vines and fruit trees, or Downy Mildew on cucumbers.
Genetically Modified Organisms (GMOs) - Agricultural crops can be genetically modified to make them more resistant to pests and diseases, or tolerant to certain herbicides. For example, a gene from the bacterium Bacillus thuringiensis can be incorporated into cotton to provide protection against the larval stages of the cotton bollworm and native bollworm.
GMOs are regulated by the Commonwealth Government through the Office of the Gene Technology Regulator (OGTR) under the provisions of the Gene Technology Act 2000. Where a genetically modified product is determined to be a pesticide, it is subject to an assessment and registration process in accordance with APVMA requirements.
Herbicides -shy; These destroy, suppress or prevent the spread of a weed or other unwanted vegetation, for example, the herbicide glyphosate is used to control a range of weeds in home gardens, bushland and agricultural situations.
Insecticides -shy; These destroy, suppress, stupefy, inhibit the feeding of, or prevent infestations or attacks by, an insect. Insecticides are used to control a wide variety of insect pests, including thrips, aphids, moths, fruit flies and locusts. Pesticides include products used on animals to control external parasites if they require dilution or mixing with water. Products applied directly to animals without dilution, injections or other medicines administered internally to treat animals are veterinary medicines and are regulated by the department of environment.
Lures -shy; These are chemicals that attract a pest to a pesticide for the purpose of its destruction. Solely food-based lures, for example cheese in a mousetrap, are excluded and are not considered pesticides.
Rodenticides -shy; These are chemicals used specifically for controlling rodents such as mice and rats.
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Repellents -shy; These repel rather than destroy a pest. Included in this category are personal insect repellents used to repel biting insects.
A number of living organisms that can control pests have also been registered as pesticides. Rabbit Haemorrhagic Disease, for example, has been used to control rabbit numbers; and bacteria that act as biological insecticides have been used to control various insect larvae, such as moths and mosquitoes.
'Natural' pesticides
Many natural substances can be used as pesticides, such as extracts of pyrethrum, garlic, tea-tree oil and eucalyptus oil. When these natural chemicals are used as pesticides they become subject to the same controls as pesticides produced synthetically.
Common misconceptions
The term pesticide covers a wide range of substances that are used for the control of pest species.
A common misunderstanding is that the Pesticides Act 1999, which controls the use of pesticides, does not apply to the use of herbicides. This misunderstanding arises because the term pesticide is sometimes wrongly used to describe insecticides only. The legal definition of a pesticide (below) under the Pesticides Act does, in fact, cover herbicides, insecticides, fungicides, rodenticides and many other types of substances.
Definition
Under the Pesticides Act 1999, a pesticide is an 'agricultural chemical product' as defined in the Agricultural and Veterinary Chemicals Code Act 1994 (Cwlth), namely:
'a substance or mixture of substances that is represented, imported, manufactured, supplied or used as a means of directly or indirectly:
1. destroying, stupefying, repelling, inhibiting the feeding of, or preventing infestation by or attacks of, any pest in relation to a plant, a place or a thing; or
2. destroying a plant; or 3. modifying the physiology of a plant or pest so as to alter its natural development,
productivity, quality or reproductive capacity; or 4. modifying an effect of another agricultural chemical product; or 5. attracting a pest for the purpose of destroying it.'
Under the Pesticide Act 1999, some external parasite treatments are also considered to be pesticides if the product requires dilution or mixing in water before use and is not prescribed under the Stock Medicines Act 1989 as a low-risk veterinary chemical product.
Another common misconception is that pesticides made from natural substances or 'home brews' are intrinsically safer in all respects than synthetically produced or commercial pesticides. Sodium fluoroacetate (1080) occurs naturally in a number of Australian plants; however, it is a highly toxic substance that is used to kill pest animals such as rabbits, feral pigs, wild dogs and foxes. All substances whether they are synthetic or naturally derived involve some degree of risk when they are used to control pests.
TECHNICAL PAPERS
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MANAGEMENT OF WASTE WATER AND TECHNOLOGIES INVOLVED
Pollution and health impact of pesticides
Pesticides / Agrochemicals are mainly used in the agriculture and public health sector. In agriculture pesticides use to increase the crop yield. Due to increase in population, crop yield must be needed to increase. But the exposure of the pesticide both occupationally and environmentally causes a range of human health problems because pesticides are toxic in nature. The most important portion of contamination due to pesticide / Agrochemical wastewater is observed in agricultural areas and in surface waters that come from agricultural areas. The major pollution of the pesticide wastewater is released from pesticide/ agrochemical manufacturing industry wastewater.
Pesticide wastewater distinguishes itself because of its toxic and persistent nature in the environment. This wastewater depicts a wide variation in its characteristics based on the pesticide product; raw materials used and water consumption and wastewater flow. The general characteristics of the pesticides / Agrochemical manufacturing industry wastewater and its Central Pollution Control Board (CPCB) limits are shown in Table 1. The WHO limits of the pesticide residue in water to 0.1 μg/L for an individual and to a total of 0.5 μg/L for all pesticides. As per Bureau of Indian Standards (BIS) the total pesticides should be absent in drinking water and permissible limit up to 0.001 mg/L in surface water. The pesticide contamination level as high as 500 mg/L in the wastewater from agricultural industries and pesticide manufacturing or formulation plants. In addition Central Pollution of Control Board (CPCB) of government of India gives the following standards for pesticides in wastewater of pesticides manufacturing and formulation industry: Benzene Hexachloride, Carbonyl, DDT, Endosulfan, Fenitrothion, Malathion, Phorate, Methyl Parathion and Pyretrums (10 mg/L); Copper Sulphate (50 mg/L); Dimethoate (450mg/L); Zirum (1000 mg/L); Sulphar (30 mg/L); Proponil (7300 mg/L); Paraquat (2300 mg/L); All other pesticides (0.1 mg/L).
Table 1 General characteristics of pesticide wastewater and its CPCB limits
The overall impact of a pesticide depends on its behavior in the environment, its toxicity and amount applied. Different pesticides pose different type of risks of the human and aquatic
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life.nSome pesticides are commonly used in India and its health effect on the human life is explained in the Table 2.
Table 2 Most commonly used pesticides and their Health effects
In recent years, membrane technologies such as nanofiltration, reverse osmosis, electrodialysis has become a more attractive for water treatment as compared to the conventional purification. These are the pressure-driven separation technologies and only membrane distillation (MD) is a thermal-driven separation process. MD separation process is driven by the vapor pressure difference across the porous hydrophobic membrane surfaces. It is a non-isothermal membrane separation process, in which feed water is heated to increase its vapor pressure, which generates the difference between partial pressure on both sides of the membrane. MD is supposed to have a great potential due to lower energy requirement, low cost, low operational pressure as compared to RO and distillation. It utilizes low grade waste steam / heat from power stations. It allows a theoretical 100% separation factor of non-volatile solute. Due to the number of such advantages, MD is an interesting and growing technology in water treatment.
Table 3 Innovative pesticide wastewater treatment techniques
Technique Description Disadvantages
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Incineration It is a high temperature oxidation process. Pesticides are converted into inorganic gases. >99.9 % organic pesticide removal is possible.
Operated higher than 1000 0C; Formation of corrosive and toxic gases
Ozonation / UV radiation The use of ozone and UV radiation to enhance the oxidation of aromatic compounds. Ozonation is more effective in the presence of UV light because it can form hydrogen radicals, which are very effective oxidizing agents.
High energy consumption; Initial equipment cost is high
Fenton-Oxidation It can be used as a part of an oxidative system to treat and degrade pesticides. It consists of hydrogen peroxide and iron salts at low pHs. Organic pollutants are oxidatively degraded by hydroxyl radicals generated from hydrogen peroxide in the presence of iron ions as a catalyst.
It may result in the formation of other toxic or unwanted products
Electro-Oxidation It is an electrochemical method. It consists of carrying out the oxidation reaction at the anode where pollutants are transferred into non-toxic substances. The final products mainly CO2 and H2O.
It is useful especially in small scale facilities; formation of unwanted products; costly process
Electro-Coagulation It includes coagulation, adsorption, precipitation and flotation. It utilizes iron anode to produce iron hydroxide flocks by the reaction at the anode followed by electrolysis
Costly and energy intensive process
Phytoremediation In this method plants are used to contain and remove harmful environmental contaminants from groundwater.
It is a time consuming process; Application of this is limited to surface and subsurface soil
Photocatalytic degradation The organic contaminants destroyed in a relatively short
Useful for small scale and low concentration of
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time when the contaminated soils mixed with TiO2 and exposed to stimulate solar
radiation.
pesticides
Adsorption Pollutants are adsorbed on the surface of adsorbate using activated carbon, inorganic and organic material and naturally available material.
Byproducts for disposal; No destruction involved
Reverse Osmosis Impurities are separated by a semi-permeable membrane at a pressure greater than the osmotic pressure caused by the dissolved solids.
It is an expensive process; membrane fouling is a major issue
Electrodialysis Semi permeable ion selective membranes used. Electrical potential applied between the two electrodes causes a migration of cations and anions towards respective electrodes.
Formation of metal hydroxide, which clog the membrane; Expensive process
Nanofiltration It is a recent membrane filtration method. Nano porous membranes are suitable for a mechanical filtration with extremely small pores smaller than 10 nm.
It is a very efficient but costly process
Membrane distillation It is a thermal, vapor-driven transportation process through micro porous hydrophobic membranes. The feed water is heated to increase its vapor pressure, which generates the difference between the partial pressure at both sides of the membrane. Hot water evaporates through non-wetted pores of hydrophobic membranes
It has a great potential due to lower energy requirement, low cost, low operational pressure as compared to RO and distillation
Biodegradation It relies on the ability of microorganisms to convert organic contaminants in simple and harmless compounds to the environment.
High cost; formation of the unwanted products; relatively slow process
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1. The Determination of Organonitrogen Pesticides in Municipal and Industrial Wastewater(USA)
This method covers the determination of certain organonitrogen pesticides. Thefollowing parameters can be determined by this method:
Parameter STORET No. CAS No.Bromacil ) 314-40-9Deet ) 134-62-3Hexazinone ) 51235-04-2Metribuzin 81408 21087-64-9Terbacil ) 5902-51-2Triadimefon ) 43121-43-3Tricyclazole ) 41814-78-2
This is a gas chromatographic (GC) method applicable to the determination of thecompounds listed above in industrial and municipal discharges as provided under40 CFR 136.1. Any modification of this method beyond those expressly permittedshall be considered a major modification subject to application and approval ofalternative test procedures under 40 CFR 136.4 and 136.5.
The method detection limit (MDL, defined in Section 15) for five of the parameters arelisted. The MDL for a specific wastewater may differ from those listed,depending upon the nature of interferences in the sample matrix.
This method is restricted to use by or under the supervision of analysts experiencedin the use of gas chromatography and in the interpretation of gas chromatograms.Each analyst must demonstrate the ability to generate acceptable results with thismethod using the procedure described in Section 8.2.
When this method is used to analyze unfamiliar samples for any or all of thecompounds above, compound identifications should be supported by at least oneadditional qualitative technique. Section 14 provides gas chromatograph/massspectrometer (GC/MS) criteria appropriate for the qualitative confirmation ofcompound identifications.
2. The Determination of Organo phosphorus Pesticides in Municipal and Industrial Wastewater(USA)
This method covers the determination of certain organophosphorus pesticides inmunicipal and industrial wastewater. The following parameters may be determined bythis method.
Parameter STORET No. CAS No.Dioxathion 78-34-2EPN 2104-64-5Ethion 39398 563-12-2Terbufos 13071-79-9
The estimated detection limit (EDL) for each parameter is listed in Table 1. The EDL was calculated from the minimum detectable response of the nitrogen/phosphorus detectorequal to 5 times the gas chromatographic (GC) background noise assuming a 1.0-mLfinal extract volume of a 1-L reagent water sample and an injection of 5 μL. The EDLfor a specific wastewater may be different depending on the nature of interferences inthe sample matrix.
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This is a gas chromatographic (GC) method applicable to the determination of thecompounds listed above in municipal and industrial discharges. When this method isused to analyze unfamiliar samples for any or all of the compounds listed above,compound identifications should be supported by at least one additional qualitativetechnique. Section 13 provides gas chromatograph/mass spectrometer (GC/MS)conditions appropriate for the qualitative confirmation of compound identifications.
This method is restricted to use by or under the supervision of analysts experienced in the operation of gas chromatographs and in the interpretation of chromatograms.
3. Wastewater Analysis By Gas Chromatoghraphy/Mass Spectrometry (USA)
Introduction
Industrial and domestic waste must be managed effectively to meet the challenges ofincreasing population, stringent regulatory requirements, and aging water treatment facilities.To meet these challenges, specific analytical methods are available to monitor chemicalcompounds in wastewater. However, because of the complexity of the sample matrix, several analytical methods are required to determine polar and non-polar organic compounds in the dissolved and suspended phases that may impact water quality. This method uses representative compounds from several compound classes, to monitor unregulated and regulated contaminants.
Methods
The custom method is suitable for analysis of complex water samples such as wastewater effluents. One-liter samples, collected in amber glass bottles and stored at 4 °C, are necessary to achieve the low level of detection. Because many of the target compounds are common food additives (caffeine, butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT)), or found in detergents and plasticizers (nonylphenol-NP, NPEO), care must be taken to avoid sample contamination. Field processing blanks and method blanks are used to monitor low-level contamination of samples. To meet the needs of USGS projects, the NWQL has included several sewage indicators such as pesticides, caffeine, and alkylphenols to select USEPA targeted compounds and developed a custom wastewater method. Other semi-volatile organic compounds that have been detected frequently in samples at the NWQL since 1995 were also added to the method even though manyare currently unregulated.
Samples are extracted by continuous liquid-liquid extraction (CLLE) using methylenechloride as the extraction solvent. The unique design of the extractor (fig. 1) uses a porous glass frit that disperses methylene chloride solvent in micro-droplets, improving extraction efficiency compared to conventional designs. Extraction of whole-waters samples by this technique has been in use at the NWQL since 1994, and CLLE has become the extraction method of choice for a wide range of polar and non-polar organiccompounds.
Once extracted, the CLLE sample volumes are reduced to 500 microliters prior to analysis by gas chromatography/mass spectrometry (GC/MS). Operation of the mass spectrometer in the selected-ion-monitoring (SIM) mode is necessary to achieve detection levels ranging from 0.05 to 0.20 micrograms per liter, which are required for most environmental samples.
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4. Biological Treatment of Industrial Wastewater Using Biosimulator (Pakistan)
In Pakistan, insecticides, particularly cypermethrin is mainly used for cotton crop protection, for forestry and public health management. Because of low water solubility and relatively high lipoaffinity, its presence indicates a strong bioconcentration potential in aquatic organisms. It is reported that cypermethrin acts on the nervous system and is toxic to bees, other beneficial insects, earthworms, fish and shrimps.
In developing countries farmers are using high amount of fertilizers and pesticides but at the expense of environment and health. These pesticides may be toxic and mutagenic and they may be bioaccumulated or biomagnified by the biota. At present, besides pesticides contamination from agricultural field, the agricultural industries are also contributing by relatively high quantities of toxic pesticides into the environment and most of them have no treatment facilities or have a grossly inadequate arrangement. The Karachi coastal region has become the dumping ground of hazardous waste, receiving huge quantities of untreated industrial and agricultural wastes. Prevention of water pollution and protection of human health and ecosystem in the country needs, an appropriate wastewater treatment system; easy to operate and suitable for environmental conditions.
Among various treatment technologies, the bioremediation technology has been found to be very effective, environmental-friendly and economical for the treatment of hazardous waste. It is well known that specific bacterial culture is capable to degrade the hazardous organic compounds if provided the right environmental conditions for their growth and metabolism. Many researchers have tried to isolate and identify the microorganisms from soil or water and then examine their biodegradation capabilities.
It has also been observed that these isolated microorganisms perform their activity efficiently in the activated sludge system. Although, most synthetic organic compounds biodegrade easily, making the biological treatment a technically feasible alternative for many environmental problems. However, in some cases, specific compounds have either resisted the biodegradation, or their degradation occurs very slowly thus make biological treatment ineffective. Therefore, it is essential for the biological treatment processes, to promote and maintain a microbial population that can metabolize the target wastes. The objective of present research study was to assess the growth and biodegradation potential of a bacterial isolate in the presence of pesticide using biosimulator (activated sludge system).
5. Treatment of agrochemical/Pesticide Wastewater by Coagulation/Flocculation Process(USA)
Pesticide/Agrochemical manufacturing industry wastewater poses pollution problems due to the toxic components, high chemical oxygen demand (COD) (6000-7000 mg/l), biochemical oxygen demand (BOD) (2000-3000 mg/l); high Total dissolved solids (TDS) (12000-13000 mg/l) and high alkaline pH in the range of 12-14. The most important portion of contamination due to this wastewater is observed in agricultural areas and in surface waters that come from agricultural areas. Major quality of pesticide pollution is released during pesticide manufacturing. Pesticide, usually have direct adverse effects on the living organisms.
Pesticides are highly toxic and carcinogenic in nature even at picogram loads.Moreover it persists in nature for long period of time. The process of pesticide removal from the industrial wastewater is of great importance because of well-known pesticide resistance to microbial degradation and has tendency to bio-accumulate in the soil fauna and flora. Pesticides are carcinogenic and mutagenic in nature. Hence biological treatment processes have their own limitations like toxicity and inefficiency in performance. Acclimatized microbial
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culture can be used for the treatment of this wastewater. At this juncture chemical coagulation, photo-oxidation, chemical oxidation, simple sedimentation, nanofiltration,adsorption etc. can be tried. But chemical oxidation and photo oxidation techniques areenergy intensive and simple coagulation methods are more suitable.
Pesticide wastewater distinguishes itself because of its toxic and persistent nature in the environment. This wastewater depicts wide variation in its characteristics based on the pesticide production; raw materials used and water consumption and wastewater flow. This wastewater has been reported to be treated by electrochemical techniques namely electro-oxidation, electro-coagulation and electro-fenton methods. Various innovative technologies have been reported in literature but they are cost intensive and are not ecofriendly in nature. A typical unit manufacturing herbicides and few chemical intermediates like metalgxyl,Dextrinol, propiconazole, hexaconazole (all herbicides) and 1, 2- Pentanediol, 2,4-Dichloroacetophenone was identified and the wastewater from this unit was collected for experimental work.
Wastewater flow of this unit is around 68 m3/day. Almost 85% of the total water is generated as wastewater. Because of the wastewater toxicity conventional biological treatment units which employ anaerobic filter, activated sludge process or trickling filters usually malfunctions, creating environmental problems. Hence, an alternative treatment process was envisaged which can be used either independently or in tandem with theconventional treatment units as pretreatment or a polishing process. One of the treatment options seemed viable for the pollution abatement of pesticide wastewater is physicochemical treatment.
Based on the literature review few selected common coagulates like Alum, Poly Aluminum Chloride (PAC), ferrous sulphate (FeSO4) and Polyelectrolyte were identified for the treatment. Ferrous sulphate (FeSO4), Alum, Poly Aluminum Chloride (PAC) were used independently and in combinations with the addition of Polyelectrolyte Magnafloc were studied in detail. As the pH of the wastewater was highly alkaline; Lime was not selected.The present article describes the investigation conducted in selecting coagulants andpolyelectrolyte for pesticide wastewater treatment and optimizing the conditions for successfully reducing COD, BOD, SS and TDS.
6. Combined Solar advanced oxidation and PAC adsorption for removal of pesticides from industrial wastewater(Japan)
The use of pesticides is widely increased in the last decades in intensive agriculture activities. Contamination of water streams with pesticides rich wastewater became critical and prevalent. Because of their high toxicity even at relatively low concentrations, the conventional biological treatment based on microorganism activity is not a proper technology for treatment of pesticide wastewater industry. Advanced oxidation processes (AOPs) have been realized as particularly efficient technologies for pesticides degradation. In AOPs, powerful chemical reactions with the aid of energy source are able to destroy even the most recalcitrant organic molecules and convert them into relatively benign and less persistent end products such as CO2,H2O and inorganic ions. Among AOPs diverse processes, heterogeneous photocatalysis and photo-Fenton processes using artificial or solar irradiation have been recognized to be effective for the degradation of several types of pesticides existing in industrial wastewater. In the heterogeneous photocatalysis, the ultraviolet light (λ<400nm) are utilized as an energy source and a semiconductor photo-catalyst like ZnO or TiO2. TiO2 is distinctive with high surface area, good particle size distribution, excellent chemical stability, and the possibility of using sunlight as a source of irradiation.
For photo-Fenton process, Fe2+ or Fe3+ and H2O2 are a source of hydroxyl radicals (HO•). The basis of the chemistry is the Fenton reaction (Fe2+ +H2O2) which produces HO• and results in oxidation of the Fe2+ to Fe3+. The photo-Fenton reaction typically provides
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enhanced rates and a faster mineralization of recalcitrant organics than the dark reaction and can take the advantage of UV irradiation from the solar light. In the reaction of the photo-Fenton process Fe2+ ions are oxidized byH2O2 to Fe3+ and one equivalent HO• is produced. In aqueous solutions the resulted Fe3+ act as the light absorbing species that produce another radical while the initial Fe2+ is reproduced as illustrated in the following equations:
Fe+2 + H2O2 Fe+3 + •OH + OH- (1) Fe+3 + H2O + hυ Fe+2 + •OH + H+ (2)
Even though AOPs have been recognized to be very effective in degradation of recalcitrant organics, degradation of pesticides needs longer treatment time and complete degradation is rarely achieved. In addition, their operation cost is considered to be very high. Adsorption of hazardous matter from contaminated water by activatedcarbon has been recognized to be economic and efficient technology, especially in disposing of low concentrations of organic contaminants. The systems based on activated carbon were reported to have high efficiency for removal of a wide variety of toxic pollutants. Adsorption is a physical phenomenon, depending largely on the surface area, pore size, pH, solution temperature, and the nature of adsorbent and its substituent groups. Removal of the pesticides by activated carbon was recently reported to be effective. For instance, Gupta et al. reported that Methoxychlor, atrazine, and methyl parathion were eliminated by powdered activated carbon made from waste rubber tire with efficiency of 91%, 82.1% and 71.78% respectively. Moreover, Moussavi et al. showed that Diazinon is removed with efficiency of 98% by adsorption onto NH4Cl induced activated carbon. Also, Jusoh et al. found that Malathion could be adsorbed on the granular activated with adsorption capacity of 909.1 mg/g. Accordingly, the results concluded from the literature demonstrate the good potential of applications of activated carbon adsorption for the removal of pesticides. The present study aims to investigate the treatment of wastewater containing Lambda Cyhalothrin, Chlorpyrifos, and Diazinon by two stages of treatment. The 1ststage is advanced oxidation using TiO2 solar photocatalysis, versus solar photo-Fenton reaction. The 2nd stage is adsorption by commercial powdered activated carbon (PAC). The effect of contact time, pH, and PAC adsorbent dose were evaluated. Moreover, the experimental data were analyzed by the Freundlich and the Langmuir isotherms. Also, Pseudo 1storder and pseudo-second order kinetics models were tested for describing the adsorption kinetics.
7. Removal of pesticides from wastewater by electrochemical methods A comparative approach(India)
Various innovative technologies have been proposed for the removal of pesticides namely photocatalytic oxidation, ultrasonic radiation, bioremediation and thermal desorption. They are neither cost effective, nor ecofriendly, nor involving low concentrations. In recent years, there has been an increasing interest in the use of electrochemical methods for the treatment of recalcitrant toxic wastes. Electrochemical methods have been successfully utilized in the purification of olive oil wastewaters, domestic sewage, landfill leachate, tannery wastes, textile wastes. These methods are environmentally friendly and they do not form new toxic wastes. Removal of methyl parathion by about 80% was reported. Removal of pesticide wastewater by three methods was studied individually by electrooxidation process, EOP, electrocoagulation process, ECP and electro-Fenton process, EFP. Globally pesticides are toxic to non-target receptors including humans and reach them through food chain. Most of the pesticides are non-biodegradable because of their molecular structure with stable internal bonds. Pesticide pollution of natural waters has become a pervasive problem. Wastewaters from pesticide manufacturing industries originate from cleaning activities after batch operation during the synthesis processes. They may contain toxic organics and pesticide
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residues which pose a threat to the quality of surface and groundwater. Wastewaters from agricultural industries and pesticide formulation or manufacturing plants were reported to have pesticide contamination levels as high as 500 mg L-1.
The overall impact of a pesticide depends on its behaviour in the environment, its toxicity and the amounts applied. Different pesticides pose different types of risks in varying degrees like cancer and genetic effects. Their residues may persist in soil, aquatic sediment resulting in biomagnifications in the food web. Organophosphate pesticides, with stable structures at atmospheric condition can be harmful to aquatic life even at very low concentrations. For example at about 20 °C and pH 7.4, methyl parathion has a hydrolytic half-life of 108 d and similarly its toxic metabolite, paraoxon, has a half-life of 144 d. The rate of degradation increases with temperature and sunlight intensity. When large concentrations of methyl parathion reach the soil, as in an accidental spill, degradation starts after a few years. In the recent years, there is an increasing interest in the development of environmentally friendly electrochemical methods to treat toxic organic pollutants in wastewaters.
The organic and toxic pollutants present in such wastes, such as phenols which are present in many pesticides, are usually destroyed by anodic oxidation as a result of the production of oxdants such as hydroxyl radicals, ozone, etc. Treatment of concentrated wastewater is often difficult because of microbial toxicity and mass transfer limitations. In this regard, it is advisable to develop technologies that facilitate easier degradation of these biorecalcitrant organic compounds. The studies of using electrochemical methods for reduction of pesticides are of interest. EOP, EFP and ECP appear to be promising means to solve the environmental problem generated by the discharge of these effluents. Our current work involves the removal of pesticides from the samples collected from a nearby manufacturing industry by EOPs, EFP and ECP. The removal of pesticides by each of these methods with impact of initial pH was evaluated. The Fourier transform infrared spectroscopy (FTIR) spectral variations during the processes of degradation of methyl parathion, atrazine and triazophos were discussed in this paper.
8. Use of Fenton's Reagent for Removal of Pesticides from Industrial Wastewater (Poland)
The process of pesticide removal from industrial wastewater is of great importance because of well known pesticide resistance to microbial degradation, and its ability of cumulation in the environment as well as possible carcinogenic and mutagenic properties. One of the possible methods of their degradation and removal is chemical oxidation, especially advanced oxidation processes (AOPs) using e.g. O3/H2O2 (Peroxone), O3/H2O2/UV, O3/UV, H2O2/UV, TiO2/UV and Fenton reactions. These processes involve the in situ formation of highly reactive hydroxyl radicals (OH), which react quickly andnon-selectively with almost all-organic pollutants. Fenton's reaction is one of the most effective methods of oxidation of organic pollutants, that are oxidatively degraded by hydroxyl radicals generated from H2O2 in the presence of Fe2+ as a catalyst:
Fe2+ + H2O2 -> Fe3+ + OH + OH- (1)
When ferrous salts are used, the hydroxyl radical is produced immediately by the rapid reaction between ferrous ion and hydrogen peroxide (Equation 1). With ferric salts, the hydroxyl radical is produced in a two-stage process with the slow reaction between ferric ion
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and hydrogen peroxide (Equation 2) followed by the rapid reaction between the produced ferrous ion and additional hydrogen peroxide:
Fe3+ + H2O2 -> Fe2+ + HO2- + H+ (2)
The efficiency of Fenton's process depends on H2O2 and Fe2+ concentrations and pH of the reaction. According to a previous researcher's report, pH value should be inthe range of 3 to 5. Fenton's reagent was found to be very effective in treating various industrial wastewater components, including aromatic and aliphatic compounds, a wide variety of dyes, as well as many other substances, including pesticides [19, 20]. Fenton's reagent has been applied in the decomposition of atrazine [2- chloro-4-(ethylamino)-6-(isopropylamino)-j-triazine], which is a potential carcinogenic compound relatively resistantto conventional oxidation methods such as ozonation or chlorine dioxide action and of a high persistence in the environment. The aim of the present study is to determine the efficiencyof Fenton's reaction in the process of pesticide removal from wastewater produced by a chemical factory located in southern Poland. Various organochlorine pesticides and their derivatives, i.e. γ-HCH (Lindan) and its inactive isomers (α- and β-HCH), DDT, DMDT (Methoxychlor) as well as organophosphorous pesticides, i.e. fenitrothion and chlorfenvinphos were the subject of experiments.
9. Treatment of Pesticides Industry Wastewater by Water Hyacinth (Eichornia crassipes) (Ethiopia)
Industrialization is backbone for growth of any country. So many industries are running which are responsible for environmental disturbance. The disturbances are may be untreated waste which generated from process, production, cleaning or washing purpose (Celis et al., 2008). The waste generated from the industries creates serious effect on living thing existing on the earth. Some waste that much toxic in nature that it will damage for long life. In those categories pesticide industries play an important role (Cooke et al., 2004). Several hundred pesticides of different chemical nature are currently used for agricultural purposes all over the world. Because of their widespread use, they are detected in various environmental matrices, such as soil, water and air (Laperton, 2006). Pesticides are divided in to many classes, of which the most important are organochlorine and organophosphorous compounds. Organochlorine pesticides are known to resist biodegradation and therefore they can be concentrated through food chains and produce a significant magnification of the original concentration at the end of the chain (Mascolo et al., 2001). The general progression of pesticide development has moved from highly toxic, persistent and bio-accumulating pesticides such as DDT, to pesticides that degrade rapidly in the environment and are less toxic to non-target organisms. The developed countries have banned many of the older pesticides due to potential toxic effect to man and\or their impact on ecosystems, in favour of more pesticide formulations (Perrin-Ganier et al., 2001). In the developing countries, however, organochlorine pesticides still remain the cheapest to produce and, for some purposes, remain highly effective.
Developing countries maintain that they cannot afford, for reason of cost or efficacy, to ban certain older pesticides. The dilemma of cost/efficacy, versus ecological impacts, including long range transport, and access to modern pesticides formulations at low cost remains a contentious global issue (Wang and Li, 2008). Pesticide residues reach the aquatic environment through direct runoff, leaching, and careless disposal of empty container, equipment washing etc (Milindis, 1994).
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Surface water contamination may have ecotoxicological effects for aquatic flora and fauna as well as for human health if used for public consumption (Balkrishnan et al., 2011). Sediments are ecologically important components of the aquatic habitat, which play a significant role in maintaining the trophic status of any water body . Highly polluted sediments are adversely affecting the ecological functioning of rivers due to persistence in the environment and longrange transport (Singh et.al, 2005).
Pesticides played a vital role in the economic production of wide ranges of vegetable, fruit, cereal, forage, fibre and oil crops which now constitute a large part of successful agricultural industry in many countries. They lower crop losses, increase revenue to farmers from the additional marketable yield obtained with their use and thus lower the cost of production per unit output (Singh et al., 2004). Other benefits include: 1) reduced uncertainty of crop loss from pests, 2) increased profit to farm input suppliers (machinery, fertilizer, chemicals and seed companies) from increased sale, 3) benefit to consumers through de- creased price of raw foods or improved quality of food products and 4) benefit to society as whole (farmers, consumers, farm suppliers, food processors) from increased employment opportunities and expanded export of food products (Beg and Ali, 2008). Various innovative technologies have been reported in literature like inceration (Felsot et al., 2003), Ozone treatment (Shang et al., 2006), Hydroyslis(Badawi et al., 2001), Adsorptions (Chowdhury et al., 2011), Coagulation (Misra et al., 2013)etc, but they are cost intensive and are not ecofriendly in nature[7, 8, 9]. Other alternative for waste water treatment like aquatic weeds Eichhornia crassipes (water hyacinth) or Pistias stratiostes (water lettuce) are also present in literature due unawareness the method was ignore. With scientific design and proper care it shows better efficiency for many industrial water, which is economical and ecofriendly (Hansel et al., 2001).
In this study an attempted has been made to reduce the physicochemical parameters of the pesticide by aquatic weed. Water hyacinth was choosing as treatment material for waste water. The reduction of chemical oxygen demand, biological oxygen demand, total phosphorus, nitrogen, dissolved solid and suspended solid was examine with retention time. During the experiment time increase or decrease in dry weight, total amino acid, protein and chlorophyll on water hyacinth was also studied.
Treatment Technologies
There are various treatment methods are available for the treatment of pesticide wastewater such as thermal, chemical, physical and biological methods. The most commonly used technique under thermal method is incineration. Under Chemical method, the treatment techniques are ozonation/UV radiation, fenton-oxidation, electro-oxidation, electro-coagulation, phytoremediation and photo-catalytic degradation. The techniques under the physical method are adsorption, reverse osmosis, nano filtration electro dialysis and membrane distillation. The biological method used biodegradation technique for treatment of pesticides wastewater. But these techniques are neither cost effective, nor eco-friendly, nor involving low concentration. Each technique provides a different and unique approach and perhaps provides certain advantages over others for a particular situation. However, when large volumes of water containing toxic elements are to be treated, it would be of great advantages if the method would provide reliable results without involving much cost and working efforts. The description and disadvantages of each technique for pesticide wastewater treatment are explained.
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References
1. Jilani, Seema, and M. Altaf Khan. "Biological Treatment of Industrial Wastewater Using Biosimulator." Middle-East Journal of Scientific Research 13.2 (2013): 124-32.
2. EPA Method 1657." The Determination of Organo phosphorus Pesticides in Municipal and Industrial Wastewater EPA METHOD 1657. Web. 28 Mar. 2016.
3. U.S. Environmental Protection Agency, 1996, Thirty-seventh report of the Toxic Substances Control Act Interagency Testing Committee to the Administrator: Federal Register, v. 61, no. 23, Feb. 2, 1996, p. 4188–4196.
4. U.S. Environmental Protection Agency, 1995, Methods for Organic Chemical Analysis of Municipal and Industrial Wastewaters, Code of Federal Regulations, 40, Parts 136-149.
5. Misra, R., SHANTA SATYANARAYAN, and N. POTLE. "Treatment of Agrochemical/Pesticide Wastewater by Coagulation/Flocculation Process." International Journal of Chemical and Physical Sciences 2.1. 2013.
6. Malato, Sixto, Manuel I. Maldonado, Isabel Oller, and Ana Zapata. "Removal of Pesticides from Water and Wastewater by Solar-Driven Photocatalysis." SpringerBriefs in Molecular Science Emerging Compounds Removal from Wastewater (2012): 59-76.
7. Hermosillo, Oscar Monroy, and Sofia Sarquis. "Design Considerations for Waste Water Treatment with Water Hyacinth E. Crassipes." Environmental Technology 11.7 (1990): 669-74.
8. Adamczyk, Dagmara. "Use of the Fenton Reagent - Regenerated Activated Carbon for Treatment of Wastewater from the Textile Industry Zastosowanie Zregenerowanych Reagentem Fentona Węgli Aktywnych Do Oczyszczania ścieków Z Przemysłu Tekstylnego." Chemical Review Przemysł Chemiczny 1.5 (2015): 52-57.
9. Adamczyk, Dagmara. "Use of the Fenton Reagent - Regenerated Activated Carbon for Treatment of Wastewater from the Textile Industry Zastosowanie Zregenerowanych Reagentem Fentona Węgli Aktywnych Do Oczyszczania ścieków Z Przemysłu Tekstylnego." Chemical Review Przemysł Chemiczny 1.5 (2015): 52-57.
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Appendices
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