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During the last three decade, a variety of pharmaceuticals traces have been discovered in the environment (Kummerer, 2001). Pharmaceutical has exposed to the environment as parent compounds or their metabolites (Ternes et. al, 2001). They are affecting the ecosystems through the change of physical and chemical behaviour which can cause biological effect by interruption the chain food (Halling-Sørensen et. al, 1998). Pharmaceutical wastes end in the aquatic environment such as river, lake, sea and ground water reaching our drinking water that may influence the human health (Webb et. al, 2003). Expire medicine may transform to toxic compound that may effect our health. Thus, it has become an increasing concern over the recent years on pharmaceuticals waste which is a normally released into the environment following their ingestion and subsequent excretion via the wastewater treatment network. Furthermore, the disposal of unused or expired medicines can also contribute to the dilemma, such as no rule for collecting the expire medicine, or there is no defined treatment of dispose these medicine. Animal medicines are another source of pharmaceutical waste in the environment such as livestock treatment, aquaculture and fishery.
Wastewater treatment technology has been considered to solve the problems of nutrient enrichment and microbial contamination, while more recent advancements have concentrated on nitrogen and phosphorus removal (Jones et al. 1998; Randall and Sen 1996; Rogalla et al. 2006; Sriwiriyarat and Randall 2005; Sriwiriyarat and Randall 2005). However, there are other compounds, such as pharmaceuticals, which may not be removed by these systems, leading to their discharge into the aquatic environment. (Giger et al. 2003; Hirsch et al. 1999; Sacher et al. 2001).
Over recent years, the water companies and regulators are interested in becoming increasingly concerned about reports of concentrations of pharmaceuticals in wastewater, as well as in the aquatic environment on a large scale, such as streams, rivers, groundwater, drinking water (Ayscough et al. 2000; Hilton et al. 2004; Kanda et al. 2003; Stokes and Churchley 2006; Thompson et al. 2005). Additional tertiary wastewater treatments, such as ozonation or granular activated carbon and chlorine dioxide treatment are expensive to install and operate. The optimisation of current treatment technologies to maximize removal of pharmaceuticals, if possible, could reduce the need for tertiary treatments. The sewage treatment processes with the most potential for optimisation are the secondary biological processes, since this is where the majority of pharmaceutical removal is seen to occur (Boyd et al. 2005; Carballa et al. 2005; Jones et al. 2005; Miao et al. 2005; Nakada et al. 2006; Perez et al. 2005; Ternes et al. 2004; Verenitch et al. 2006).
There was an increase in all parts of the world in the number and size of wastewater treatment plants, using reverse osmosis technology to produce high quality water recycled over the two past decades. As the RO water production increase, the disposal increase in the environment
Wastewater is water discharged by domestic residences, commercial properties, industry, and agriculture and can encompass a wide range of potential contaminants and concentrations. It refers to municipal wastewater, which contains a wide range of pollutants from the mixing of waste water from different sources.
Wastewater come from Human waste such as faces, urine, washing water (personal, clothes, floors, dishes, etc.), surplus manufactured liquids from domestic sources (drinks, cooking oil, pesticides, lubricating oil, paint, cleaning liquids, etc.).
Industrial site drainage such as cooling waters contain silt, sand, alkali, oil, and chemical residues; Organic bio-degradable waste, including waste from abattoirs, creameries, and ice cream manufacture; Organic non bio-degradable or difficult to treat waste such as pharmaceutical and pesticidal manufacturing.
The presence of trace organic pollutants in wastewater has been the cause of increasing public concern in recent decades due to potential health risks. Effluent Organic Matter in wastewater consists of both particulates and dissolved substances, which has been found to include several trace organic contaminants, including endocrine-disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) (Halling-Sorensen et al., 1998; Daughton and Ternes, 1999; Snyder et al., 1999, 2001d; Vanderford et al., 2003).
The compositions of wastewater differ varies considerably and it may include:
Water (> 95%) which is often added during flushing to carry waste down a drain.
Organic particles such as faces, hairs, food, vomit, paper fibers, plant material, humus, etc.
Soluble organic material such as urea, fruit sugars, soluble proteins, drugs, pharmaceuticals, etc.
Inorganic particles such as sand, grit, metal particles, ceramics, etc.
Soluble inorganic material such as ammonia, road-salt, sea-salt, cyanide, hydrogen sulfide, thiocyanates, thiosulfates, etc.
Gases such as hydrogen sulfide, carbon dioxide, methane, etc.
Emulsions such as paints, adhesives, mayonnaise, hair colorants, emulsified oils, etc.
Toxins such as pesticides, poisons, herbicides, etc.
The principal physical characteristics of wastewater are its solids content, colour, odour and temperature. The total solids in a wastewater consist of the insoluble or suspended solids and the soluble compounds dissolved in water. Suspended solids can be count in an average wastewater between 40 and 65%. This can be removed by sedimentation.
Colour is the distinctive quality that could be used to assess the overall situation of wastewater. Light brown in colour is revealed to less than 6 h old Wastewater, whereas, light to medium grey colour is revealed that wastewaters have undergone some degree of decomposition. Finally, dark grey or black colour, wastewater is having undergone extensive bacterial decomposition under anaerobic conditions. This cause the formation of various sulphides.
odour determination has become increasingly important, due to the concerned of general public with the proper operation of wastewater treatment facilities. a variety of odorous compounds are emitted when wastewater is treated biologically under anaerobic conditions. The main odorous compound is hydrogen sulphide.
Other compounds, may also cause a rather offensive odour such as indol, skatol, cadaverin and mercaptan, formed under anaerobic conditions or present in the effluents of pulp and paper mills (hydrogen sulphide, mercaptan, dimethylsulphide etc.),.
The wastewater temperature is very important to measure because most wastewater treatment include biological processes that are temperature dependent. The temperature of wastewater will differ from season to season and also with different regions. In cold regions the temperature may be between 7 to 18 Â°C, while in warmer regions the temperatures may be 13 to 24 Â°C.
Chemical and biological characteristics
It is very important to know the chemical composition of the wastewater, because it allows us to understand the reactions and interactions with the organic and inorganic compounds. The most important chemical characteristics of the wastewater are divided into two categories: inorganic and organic.
The organic composition of wastewater is a reflection of the influent water usage such as industrial, domestic, and agricultural activities. The organic composition of wastewater is approximately 50% proteins, 40% carbohydrates, 10% fats and oils, and trace amounts (e.g., Î¼g/L or less) of priority pollutants, surfactants, and emerging contaminants. The major macromolecules in BTSE are the polysaccharides, proteins, lipids, nucleic acids, and NOM (Levine et al., 1985). EfOM in the range from 103 to 106 Da include humic acids and fulvic acids present in drinking water. Wastewater compounds smaller than 103 Da include carbohydrates, amino acids, vitamins, and chlorophyll.
The inorganic compositions of wastewater are ammonia, organic nitrogen, nitrites, nitrates, organic phosphorus and inorganic phosphorus. Nitrogen and phosphorus are important because these two nutrients are responsible for the growth of aquatic plants.
Other chemical characteristics such as chloride, sulphate, pH and alkalinity, are performed to assess the suitability of reusing treated wastewater and in controlling the various treatment processes.
Trace elements are a factor in the biological treatment of wastewater. Because all living organisms require varying amounts of some trace elements, such as iron, copper, zinc and cobalt, for proper growth. But heavy metals can also contribute toxic effects. Many of the heavy metals are also classified as priority pollutants
Wastewater gases, such as hydrogen sulphide, oxygen, methane and carbon dioxide. The presence of hydrogen sulphide needs to be determined not only because it is an odorous gas but also because it can affect the maintenance of long sewers on flat slopes, since it can cause corrosion. Measurements of dissolved oxygen are made in order to monitor and control aerobic biological treatment processes. Methane and carbon dioxide measurements are used in connection with the operation of anaerobic digesters.
The biological composition of domestic wastewater often contains viruses, parasitic worms; bacteria, protozoa, insects, arthropods, and small fish. The constituents that are found in BTSE are shown in Figure 1. The fraction of particulate organic material measured as suspended solids (SS) includes protozoa, algae, bacterial floc and single cells, microbial waste products, and other miscellaneous debris. Dissolved organic matter (smaller than 0.45 Î¼ m) are typically cell fragments and macromolecules.
FIGURE 1. Typical organic constituents in BTSE and their size ranges. Adapted from Levine et al. (1985).
Pharmaceutical wastes characteristics
In Domestic wastewaters
In pharmaceutical industry
Treatment of pharmaceutical wastewaters
Disposal of pharmaceutical wastes
Disposal into waters
Disposal on land
Fate of pharmaceutical wastes in the environment
There are many of the researches and studies focusing on the detection of pharmaceutical residue in the environment, raising the claim of the hazard of pharmaceutical waste in the environment. The existences of pharmaceutical residues have been investigated such as in pesticide. To date, there are considerable data about the occurrence of antibiotics in the environment.
A study done by Fielding discovers some pharmaceuticals and related compounds in a river and drinking water (Fielding et. al, 1981). Tetracycline and theophylline were the first reported pharmaceuticals in the environment, it was an antibiotic found in a water river in 1983 (Watts et. al, 1983) used to treat infection in fish farms. Fish farms expose to the receiving waters a large portion of drugs. Because most of the antibiotics and chemotherapeutics used is not eaten by the fish, but falls through the cages and accumulates on the sea bed (Jacobsen & Berglind, 1988) and may affect the aquatic organisms. Study has concluded that 80 % of drugs used in a fish farm end up in the environment, found drug concentrations with antibacterial activity in the sediment underneath the fish farms (Samuelsen et. al, 1992).
Other pharmaceutical compounds discovered in the environment were steroids which is a physiologically active drug present in the sewage effluent (Daughton & Ternes, 1999). In addition, analgesics drug acetaminophen, stimulants caffeine, and non steroidal anti-inflammatory agents ibuprofen and aspirin, have been found in municipal wastewater (Metcalfe et. al, 2003; Boyd et. al, 2003). The presence of pharmaceutical in sewage, due to the drug is not completely degraded in the human body and excreted from the human body without any change in the chemical structure or the drug is transformed to more active compound.
The discovery of pharmaceutical in wastewater is due to the excretion of medicine by the human body into wastewater. However, there is also another source of pharmaceutical waste in the environment by disposing in the landfill. Holm et. al, (1995) report findings organic compounds from waste of the pharmaceutical industry in the bottom of a landfill such as sulfonamides, propylphenazone, and 5,5-Diallylbarbituric acid which may have entered the surrounding aquifers (Holm et. al, 1995).
Study by Eckel et. al, 1993 on a landfill in Florida received wastes between the period 1968 and 1969 from the naval base hospital, show the presence and persistence of pentobarbital, meprobamate and phensuximide in a nearby shallow ground water (Eckel et. al, 1993). Stan et al. 1994 report that tap water in Berlin is contaminated by clofibric acid which is metabolite of a blood lipid regulator in human medical care (Stan et. al, 1994). The study shows that all samples from tap water, surface water, and several rivers in Germany are contaminated by clofibric acid in concentrations between 10 and 165 ng/I.
In agriculture application they discover chlortetraeyclines in the soil which amended with poultry manure which may develop drug resistance in livestock micro flora (Warman & Thomas, 1981). As a consequence, the pharmaceutical used for animals as growth promoters may affect micro-organism, and it may also mineralized and reach the groundwater.
The occurrence of pharmaceutical residues in the environment effected by main factors, the amount of pharmaceutical and the fate of each compound in both of the sewage treatment plants and the aquatic environment. The fate of the pharmaceutical waste in the environment may be proceeding to three possible fates:
It may ultimately mineralise to carbon dioxide and water, e.g. aspirin (Richardson & Bowron, 1985).
It may will be retained in the sludge because is lipophilic and not readily degradable.
It may metabolise to a more persistent hydrophilic compound and pass the waste water treatment plant then discharge to aqua and may affect the organisms if it is biologically active e.g Clofibratc (Richardson & Bowron, 1985).
Sources of pharmaceutical wastes
Biodegradability of pharmaceutical wastes
Detection methods of pharmaceutical wastes
Routine analysis (COD, BOD, TOC,â€¦â€¦)
Over the years, a number of different tests have been developed to determine the organic content of wastewaters. In general, the tests may be divided into those used to measure gross concentrations of organic matter greater than about 1 mg/l and those used to measure trace concentrations in the range of 10-12 to 10-0 mg/l. Laboratory methods commonly used today to measure gross amounts of organic matter (greater than 1 mg/l) in wastewater include (1) biochemical oxygen demand (BOD), (2) chemical oxygen demand (COD) and (3) total organic carbon (TOC). Trace organics in the range of 10-12 to 10-0 mg/l are determined using instrumental methods including gas chromatography and mass spectroscopy. Specific organic compounds are determined to assess the presence of priority pollutants.
The BOD, COD and TOC tests are gross measures of organic content and as such do not reflect the response of the wastewater to various types of biological treatment technologies. It is therefore desirable to divide the wastewater into several categories, as shown in Figure 18.1.
Advanced analysis GC-MS and LC-MS
Most of the studies recorded on detection and quantifying fate of pharmaceutical waste in the environment are done on cold and wet countries while there are no studies on the hot dry countries such as Kuwait. Thus, there is a need for research on hot dry countries to assess fate of pharmaceutical waste in the hot dry climate. Different factor may affect on the medicine compounds, these factor could be physical and chemical such as radiation, humidity and temperature. Photo chemical (photolysis) reaction may transform it to a toxic or degraded to less harmful compound which this study wants to investigate. The climate in Kuwait and other Arabian Gulf countries are hot and dry, so they are perfect for the study of fate of pharmaceutical in the extremely hot dry environment.
The disposal method and quantity of unused or expired pharmaceuticals in Kuwait and other Arab countries are not known. They disposed the medicine with other municipal waste in the same landfill. An inappropriate disposing may cause health problem (e.g. mixing dangerous medicine such as used in cancer with other volatile compound).
The Kuwait government spends in 2008 around 298 million dollar in pharmacy. Government health centres provide the majority of the population in Kuwait where private pharmacies provide a less portion of people. Because of the free medication from the government, so the high proportion of public health systems derived medicines could be a reflection that this is where most patients obtain their medicines.
A study on Arabian Gulf Countries households in 2001 established that 25 % of medicine is hold in home until expire (Abu Auda, 2003). The same scenario may it happens in Kuwait which can be estimating to expire in medicine around 74 million dollar yearly. Thus, medicine expired with an average value of 25 dollar per person increase the caution about the pharmaceutical waste in Kuwait for 3 million populations. In the United Kingdom, a study in 1996 estimated that £37 million of unused medicine in households (Hawksworth et. al,1996) where in the United States, the value of unused medicines was over $1 billion per year for mature patients alone (Morgan, 2001) and in Texas estimated that pharmaceutical waste is $106 million per year (Garey et. al, 2004).
This study will be focusing on the detection medicine in wastewater plant and landfill in Kuwait and further investigation will be done in groundwater for the contamination from the wastewater and landfill (containing medicine waste). Further, research will be done on the biodegradation process that exploring the degradation of the medicine and how can improve this process.
The benefit of study is to provide a database of pharmaceutical waste and tracking the movement of this waste for precaution of any health and environment problems. Develop new process for bioremediation of pharmaceutical waste.
Materials and Methods
Tracking of Pharmaceutical wastes in WWTP
Pure culture studies
Treatability in bioreactors
Routine analysis of wastewater (standard methods)
Advanced analysis (GC-MS & LC-MS)