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Being an essential trace element, copper (Cu) is always involved for many biological processes because its own important role for catalytic cofactor in oxidative enzymes (Puig and Thiele, 2002). Thus, copper is needed by organisms to function their metabolisms at sufficient concentration. According to WHO (1998) daily requirements of copper for human is 1.2 - 1.3 mg Cu/day for both adult women and men. However, deficiency and excess of copper causes toxicity for organisms. Several adverse effects have been delivered to human and other organism as well as environment. Exposure of copper on human will cause accumulation in their gastrointestinal, liver, kidney, brain and also eyes (WHO, 2004). In addition, Menkes syndrome, Wilson disease and Indian Childhood Cirrhosys are determined as genetic disorders related to metabolism of copper.
In environmental system, copper can be present in soil, air and water body. Although presence of copper originate from natural sources which are caused by precipitation and weathering processes, anthropogenic sources declare as mainly sources of copper. Naturally, copper present in aquatic system in low concentration. Since contribution of industry discharged and sewage treatment plants, agriculture and mining activities make abundance of copper in the aquatic environment at the high concentration. This condition makes copper classified as common pollutant in water body. According to Calle et al (2007) corrosion of plumbing makes extremely availability of copper in drinking water whereas US EPA has been set up standard of allowable copper in drinking water not more than 1.3 mg/l.
Various concentration of copper and its bioavailability in the aquatic environment related to several factors such as water hardness, pH, organic ligands, suspended particulate matter and carbonates through complexation, precipitation and adsorption. Copper which release to the aquatic system occurs in form of free ionic cupric cation (Cu2+) and soluble complexes. In state of Cu(II) ion, copper forms coordination compounds or complexes with both inorganic and organic ligands. Its form becomes important oxidation state of copper in natural aquatic environments due to its highly reactive characteristic. Thus, Cu(II) ion is classified as most toxic species in the aquatic environment.
Currently, there are several methods which develop to detect Cu(II) ion due to not only its environmental importance but also being as toxic element. GFAAS, ICP-MS and ICP-OES are considered as the common methods for trace metal analysis including Cu(II) ion analysis (Carrilho et al., 2003; Mannio et al., 1995). Those methods rely on absorbed or emitted electromagnetic of atom. Information of wavelength of absorbed or emitted radiation as well as its intensity determine characteristic of each element and its concentration. Instead of measurement of an element, ICP-MS and ICP OES capable to detect multi element and their concentrations simultaneously at high and sub ppb detection limit (Perkinelmer, 2009). Unfortunately, these methods are classified as expensive methods because of using highly technological instruments and complicated method to operate the instruments.
Thus, a chemosensor has been introduced to overcome limitations from others methods in analysis of Cu(II) ion. A chemosensor is a chemical sensor that detects and recognizes the analytes and changes its physical property upon interaction between sensor and analytes. The changing of physical property involves color changes as well as fluorescent emission of the sensor which can be detected easily. A chemosensor which introduces color changing during reaction process is called colorimetric chemosensor. Another sensor which induces fluorescent changes has been known as fluorogenic chemosensor.
Unlike fluorogenic chemosensors which are required the instruments to detect fluorescent emission, colorimetric chemosensors offer effortless detection method (Lu, 2009). Naked eye can be signaled whether any presence of trace elements including Cu(II) ion due to color changing. Thus, there is increasingly demand to develop many researches regarding to colorimetric sensor. Of many researches have been conducted, Pyrazolidine Luminol (PL) is found as a colorimetric chemosensor. This sensor has been identified as a selective sensor for Cu(II) ion. Using this sensor, the presence of Cu(II) in aqueous can be detected directly by naked eye. Upon binding between the sensor and Cu(II) ion, it induces the change of color from pale yellow to dark green.
A study about Pyrazolidine Luminol (PL) as a colorimetric chemosensor for Cu(II) ion detection in term of environmental application is focused. The aim of this study is to develop a colorimetric chemosensor for the detection Cu(II) ion contaminated in water and wastewater. Detection limit of this sensor is important to define. For applicable purpose, the sensor strip is designed by coated pyrazolidine luminol over the silica plate. The binding between Pyrazolidine Luminol and Cu(II) ion on silica plate will induce the change of the color. This study is expected to create a new sensor for Cu(II) ion based on Pyrazolidine Luminol for sensitive and selective detection of Cu(II) ion contaminated water.
1.2 Statement of problems
Copper as a trace element is present in the environment. Soil, sediment, seawater, ground water, surface water and drinking water contain amount of copper at various concentration. Presence of copper can be over allowable standard which had set up by government or organization such as WHO and US EPA. This condition occurred because other sources generated copper in high amount. For instance, electroplating, paint and electronic industries generated wastewaters which have high copper. Particularly in the aquatic environment, copper was available in soluble form. In this form, copper was taken up by animals, plant, algae and bacteria form, and then give harmful effect to them. For instance, copper sulphate used to apply as algae control in the lake. Moreover, It was a great concern to recognize concentration of copper in the environment especially in aquatic environment due to its toxicity to environment as well as to human health.
Recently, technologies have been completed to detect trace element including copper. These instruments belong to high technology devices. They can be detected concentration of copper up to 0.01 Âµg/l in water sample (WHO, 1998). However, skills and knowledge are needed to operate those instruments. Not only high cost but also proper sample preparations are required to run instruments such as AAS, ICP-OES, and ICP-MS (Davidowski, et al., 2007; Eletta, 2007). Those instruments need series of standard curve of copper for measure the water sample. Error within preparing concentration of standard curve influenced the results of measurement. Other errors of measurement used to take place during the process because of improper maintenances instrument and also human error. Due to completed procedures, not many people capable to use those instruments.
Some researches have been synthesized colorimetric chemosensor for Cu(II) ion dectection as a alternative method. Azobenzene-based receptors examined as Cu(II) ion selective colorimetric chemosensor that give a change color from red to pale yellow (Lee et all., 2007). Furthermore, synthesized of rhodamine derivative by Chen et al., (2009) proposed Cu(II) ion colorimetric chemosensor from colorless to a red color. However, a colorimetric chemosensor which can be addressed to application in water and wastewater sample is imperative to actualized due to not all of colorimetric chemosensors can be transformed into chemosensor strips. Selection of solid support, exact concentration of sensor to be coated on it and dependence of environmental parameters are some factor that affect a chemosensor strip to be effective apply in water and wastewater sample (Diez-Gil el al., 2007 ; Capitan-Valley et al., 2003)
Finally, PL sensor are found as a colorimetric chemosensor which able to change its color from pale yellow to dark green trough presence of Cu(II) ion. Hence, PL colorimetric chemosensor is studied to transform into sensor strips. It intended to be offered as an alternatively device to detect presence of copper in the aqueous environment. By coated on silice plate, this sensor is expected to catch up for field work application. It has been attempted that this device can gain its high detection limit. To detect concentration of copper in water and wastewater, it is important to create device which sensitive, can be use easily and applicable in the field study.
1.3 Objectives of the study
The objective of the study is to create chemosensor strips for Cu(II) ion presence in water and wastewater sample.
The specific objectives are
To develop a PL strip for the detection of Cu (II) ion in aqueous environment
To determine the detection limit of PL strip
To employ the PL strip for the detection of trace amount of Cu (II) ion in aqueous environment compared with the known methods, e.g. ICP-OES
1.4 Scope of the study
The scope of study is to develop new chemosensor for the detection of Cu(II) ion in an aqueous environment. Due to limited time, this study will focus to develop PL detection limit in order to achieve its highest value. The project will start from the synthesis of PL. The selectivity of the sensor for Cu(II) ion over other metals will be investigated. The detection limit of PL sensor are determined in the laboratory by use known concentration of Cu(II) ion solution. 1HNMR test and UV spectrometric analysis will elucidate the binding mechanism. Coating technique on silica plate will be used to develop a sensor strip. The samples of water and wastewater which contain Cu(II) ion will be measured using the sensor strips. Eventually, the comparison with another method is absolutely needed to ensure the efficiency of the sensor strips. Intensity of color changing reflects the concentration of Cu(II) ion detected by the sensor.
2.1. Physical and Chemical Properties of Copper
Copper defines as one of most longest known of heavy metal with symbol Cu. Located on group of IB of Periodic Table, copper become the 29th element which classify as transition metal. Copper owns its atomic weight of 63.546, density of 8.9, and melting point of 1083.4Â°C. Copper gives bright metallic appearing with soft and easy to form. Moreover, the electronic configuration of copper is 1s2 2s2 2p6 3s2 3p6 4s1 3d10 which cause a partially filled d subshell. Consequently, copper delivers tendency to form complex ions and occurs oxidation states (Nriagu, 1979).
Naturally, copper compounds present in the 0, I, II, and III oxidation states. Most of Cu(I) ion are oxidized easily to Cu(II) ion while Cu(III) ion only found in few compounds due to difficulties of oxidation in this state. Moreover, Cu(II) ion plays role as important oxidation state in the aqueous environment trough become powerful oxidizing agent. The copper (II) ion shows readily distortion transition properties such as color, form of complexed and paramagnetism. Preferentially Cu(II) ion binds with both organic and inorganic ligands which cause copper in the natural samples are mostly complexed with organic compounds. These compounds are soluble in water. Dissolution of Cu(II) ion also occurs in the hydroxide, carbonate and acid which give blue green color (Wilson & Newall, 1970;Cotton & Wilkinson, 1989;WHO, 1998).
Besides found in the variety of minerals, copper becomes major component of common rocks. Copper is dispersed widely in form of minerals such as sulfides, arsenides, chlorides and carbonates. The examples of common copper minerals salts are bornite (Cu5FeS4) and chalcopyrite (CuFeS2). Chalcopyrite is most abundance due to widely distributed in rocks and concentrated in the largest copper ore deposit. In addition, copper acts as rocks- forming minerals which make igneous rocks from its trace amounts in silica minerals (Nriagu, 1979; Adriano, 1986). The summary of physical chemical properties of copper and some of its salts are presented in Table 2.1
Table 2.1 Physical and chemical properties of copper and its salts
CAS registry number
Relative molecular mass
Boiling point (Â°C)
Melting point (Â°C)
1.33 at 1870 Â°C
decomposes at 650 Â°C
decomposes at > 200Â°C
143 g/litre at 0Â°C
decomposes at 140 Â°C
at 25 Â°C
decomposes at 993 Â°C
Source : Like & Frederikse (1993)
2.2 Copper Uses
Belong to third ranking of world metal consumption, copper own high demand increasingly. During 1900 to 2000, copper consumption has reached rising demand up to 13 millions tones. It will be predicted that copper demand keep to follow increasingly trend particularly in the developing countries which concentrate on industrialization. Most of copper is used as electrical products such as cable wire since its characteristics as an excellent conductor. Durable corrosion makes copper to become common plumping material. Copper is also determined as additional ingredient in many valuable alloys. In a line with development of technology, copper is utilized in modern transportation and electronics. For instance, there were 40 pounds of copper in United Stated of luxury automobile (CDA, 2010). According to Kelly & Matos (2005) in US Geological Survey, end uses of copper are divided into five major groups; building constructions, electrical and electronics products, industrial machinery and equipment, transportation equipment and costumer general products. The number of copper consumption each group in the United Stated is explained on Figure 2.1.
Figure 2.1: Copper uses in Unites States (Kelly & Matos, 2005)
In agriculture fields, copper in form of copper sulphate have been functioned as fungicide or algaecide. This compound is able to prevent fungi-based diseased on plant as well as to inhibit rots on parts of plants. Impact of water-borne diseases can be reduced by adding copper into water. Water reservoirs also used to have copper in order to control algae growth. In addition, copper compounds have been employed many years to kill parasites in freshwater aquaculture farms and ponds (CDA, 2010). Thus, copper is recognized widely in many fields of application.
2.3 Copper in the environment
2.3.1 Sources and Origin
Copper which released to the environment comes mainly from two sources: natural sources and anthropogenic sources. In natural sources, together with other minerals, copper takes part in forming earth's crust which derived from its parent materials. In these materials, copper undergoes weathering process that becomes natural sources of copper in the soil. Precipitation, deposition and resulting of sedimentation deposit also allow copper to be distributed in the environment. In the atmospheric, copper emit into environment due to windblown dust, forest fire, volcanoes particles, vegetation, seasalt sprays, and rock degassing. Estimation of natural sources emission of copper in the atmosphere are windblown dusts, 0.9-15 Ã- 103 tonnes; forest fires, 0.1-7.5 Ã- 103 tonnes; volcanic particles, 0.9-18 Ã- 103 tonnes; biogenic processes, 0.1-6.4 Ã- 103 tonnes; sea salt spray, 0.2-6.9 Ã- 103 tonnes respectively (Nriagu, 1979). Moreover, dead organism can be defined as significant natural sources of copper in the marine ecosystem (WHO, 1998).
Anthropogenic sources give higher contribution for the presence of copper in the air, soil and aquatic environment. Copper processing operation, tobacco smoke, combustion of coal in the power plant are defined as sources of copper emission to the atmosphere. These sources are approximately three times higher than copper flux from natural sources. For instance, percentages of copper emission from anthropogenic sources are 7.4% from iron and steel production. Followed by 4.6%, 3.3%, 2.7%, and 1.9% from coal and oil combustion, zinc smelting, copper sulfate production, municipal incineration, respectively. From other sources contribute 2.3% (Lide and Frederikse, 1993).
Nriagu (1979) declares main anthropogenic sources of copper in the soil are as follows:
Mining and smelting activities
Industrial effluent and traffic
Urban development and dumped waste materials
Dust and rainfall
Sewage sludge, pig slurry and composted refuse
Fertilizer, ameliorants and pesticides
In the aquatic environment, generally copper is classified as nonpoint source which is come from anthropogenic sources. For instance, urban runoff, agricultural runoff, and boating activity are common sources of copper in received water (BSDC, 2003). Likewise Joseph (1999) the presence of copper is caused by water and waste discharge, rain water runoff, and air-borne dust. Antifouling marine paint is also declared as a way to released copper in the marine ecosystem. In addition, urban stormwater runoff also contains copper. Davis et al (2001) have estimated copper loading from various sources in urban stormwater which is 0.324 kg/ha-yr. Estimation of various sources of copper in the urban stormwater runoff is presented on Figure 2.1.
Figure 2.1: Various sources of copper in the urban stormwater runoff (Davis et al., 2001)
TBC Environmental report (2004) listed anthropogenic source contribute to South San Francisco Bay which can be represented of listed copper source in the coastal environment. Commonly, they release from shoreline activities as well as urban runoff. Various copper sources and primary copper source which release to the coastal environment are explained in Table 2.2
Table 2.2 Copper source listed
Primary copper sources
Air deposition Conveys copper from many sources
Conveys copper from many sources
Automobile dismantlers (runoff)
Commercial and residential land uses
Conveys copper from many sources
Construction activities-copper in sand
blasting slag and copper
Copper in waste materials used for surface finishes sandblasting, copper architectural
Copper algaecides (swimming pools, spas,
fountains, and ornamental pools)
Copper algaecides in water supply systems
Copper fungicides and herbicides
Copper in imported water supply
Copper in source water, copper
Brake pads, other vehicle sources
Conveys copper from many sources
Copper in wastewater (conveys copper
from many sources)
Industrial land use
Conveys copper from many sources
Conveys copper from many sources
Parking lots and maintenance yards (runoff)
Conveys copper from many sources
Spills and illegal dumping (copper contamination in motor oil, copper containing
Many copper sources
Conveys copper from many sources
Copper pipes, copper in source water, copper algaecides
Vehicle Fuels (Exhaust)
Wastewater treatment plants
Copper in wastewater (conveys copper from many sources)
Source: TDC Environmental
2.3.2 Fate and Behavior
Copper may present in the natural waters, wastewater, and industrial waste stream as well as in portable water. In aqueous environment, copper found in several forms such as insoluble, free dissolved, complexed dissolved and total recoverable. For example insoluble copper is known as copper sulfides and hydroxides (Gibbs, 1994).
Since copper releases to the aqueous environment, its availability, mobility and species forms will alter because of complexation process. Free cupric cation (Cu2+) created due to it associates with water. It will bind with inorganic ligands, mostly the hydroxyl (OH-) and carbonate ions (CO32-). Thus, water hardness play important role in this process. High of water hardness makes the more capacity of copper complexing. As the result, toxicity of copper goes down in line with increasing of water hardness. Stronger binding copper with organic compound occurs in ligands which have electron donor of O, N and S (Flemming and Trevors, 1989). These binding will transform copper speciation in aqueous environment. Moreover, pH also influences on copper speciation. According to Hong et al., (2010), soluble copper concentration is decrease half at pH 7.5. However, precipitated copper will be formed as increasing of pH. Total copper will remain stable in wide range of pH. Impact of pH on total copper, soluble copper and precipitated copper on copper speciation in a chemical-equilibrium model is presented in Figure 2.2.
Figure 2.2 : Impact of pH on total copper, soluble copper and precipitated copper (Lin et al., 2002)
As mentioned by Flemming and Trevors (1989) precipitation and adsorption processes play significant role to determine species and concentration of copper. Those processes declare as pathways to reduce concentration of copper in water column. The soluble copper stays in water column. Together with particle in suspension, copper will precipitate into sediment. Role of organic matter, oxides of iron, manganese and aluminum, interaction with other elements as copper adsorbent give great contribution to affect mobility and availability of copper in the environment (Adriano, 1986). Both inorganic sediments and organic sediment contain amount of copper which are vary in concentration and species. Copper-organic matter binding is abundance in organic sediment while cuprous salt is formed in inorganic sediment (ATSDR, 2004). Furthermore, vary oxidation state of copper in the water and sediment influences bioaccumulation copper on the biota of the water system.
Precipitation of copper in the soil occurs readily within alkaline condition. Furthermore, acid condition not only gives enhancement level of ionic copper but also maintains solubility of copper. At pH 2.8, copper undergo considerable mobilization only with prolonged leaching. Copper which presence in the top centimeter of acid soil is easy to make organic bounding, 18 % of copper stay in hydroxyl carbonate bound, 7 % was adsorption, followed by 11 % bound with other ions, 6 % irreversibly adsorbed. At pH 4.5 amount of extractable is 3 % and finally only 3 % copper stay mobile (Lide, 1997).
Cycling of copper involves several processes such as mobilization or transport, distribution and transformation which affect bioavailability and bioaccumulation of copper in the environment. Copper is released to atmospheric, aquatic and land ecosystem from both its natural and anthropogenic sources. Emission of copper to air environment occurs in particulate matter form or absorbed into particulate matter. Distance of traveling particulate matter in the air depends on sources of copper emission, its size, wind velocity and turbulence. In the atmospheric, gravitational settling, dry and wet deposition make copper to be removed (ATSDR, 2004). However, copper in the soil undergoes deposition. Not only organic matter but also carbon minerals and clay adsorb copper presence in the soil. Copper which is released to the aquatic environment is carried out to the water column and sediments by settle down, precipitate and adsorb processes (WHO, 1998). Cycling of copper in the environment is described briefly trough Figure 2.3.
Copper in freshwater
Cu in soil
Copper in groundwater
Fertilizer and waste disposal
Copper in marine
Cu in sediments
Cu in pore water
Figure 2.3: Copper cycle in the environment
2.3.3 Environmental levels
Average background concentrations of copper in air in rural areas range from 5 to 50 ng/m3 while concentration in the urban reaches below 1 Âµg/l. Sources of copper which are released to the atmosphere becomes major factors of level copper in the air. Approximately 0.036 ng/m3 copper found in the air of South Pole (Ellingsen et al., 2007). ATSDR (2004) reveals copper level in the air environment from 1 up to 200 ng/m3. This range becomes higher that reach 5000 ng/m3 in the smelters and surrounding of copper mining area.
In the coastal and estuaries, copper occurs in higher level than seawater. Copper found in the uncontaminated seawater with concentration less than 1 Âµg/l. Copper shows increasing of concentration in the near of surface seawater (less than 200 m) and steady increase in the down of seafloor (WHO, 1998). Concentration of copper in marine, oceans and estuarine of the several regions is listed on Table 2.3.
Table 2.3. Copper concentration in marine and estuarine water (Joseph, 1999)
North Sea and Baltic Sea Region
Northern Baltic Sea
Vassorfarden Bay, Findland
Kirsiu Marios Lagoon, Lithuania
Framwaren Fjord, Norway
Schelidi Estuary, Belgium
Firth of Fourth, Scotland
D(2.4 - 9.2) Âµg/L
Orient and India Ocean Region
Mekong river Coast
Saigon River Station
Erhjen Chi, Taiwan
Takasaki Seto, Japan
Uranouchi Bay, Japan
North Atlantic Ocean Region
Lavos Region, Portugal
United States of America
Pettaquamseun Estuary, RI
Mississippi River Delta, LA
Vero Beach, FL
North Contentin, France
D (ND-10.7) Âµg/L
Antarctic Ocean Indian Section
Purna River Estuary
Mindhola River Estuary
North Pacific Region
USSR, Gulf of Peter the Great
Northeast Pacific-Deep Sea
South Atlantic Region
South Shetland Islands, Antarctic
United States of America
Santa Monica Basin,
Surface Ellion Bay
T : Total copper, D: Dissolve copper
In the earth's crust, concentration of copper varies from 24 to 55 ppm. For uncontaminated soil, its median concentration reaches 30 mg Cu/kg and falls in the range 2 - 350 mg/kg (WHO, 1998). Vary concentration of copper in soil depend on its parent material characteristic and distance from anthropogenic sources, soil type and amendment. For instance, concentration copper in soil near smelters and mining can achieve to 17000 ppm. Concentration of copper in Canadian soil falls in the range 2- 100 mg/kg with average 20mg/kg (ATSDR, 2004).
For uncontaminated sediments found concentration of background copper between 800 to 5000 mg/kg. Copper levels in marine sediments range from 2 to 740 mg/kg(dry weight) (WHO, 1998). Summary of copper concentration in various sediments is formulated on Table 2.4.
Table 2.4 Copper concentrations in sediments
Source : ATSDR (2004)
Approximately 1-10 Âµg/l of concentration copper occur in the lake and river with average 4 Âµg/l (WHO, 1998). Amount of copper in ambient Canadian surface water found 0.005 mg/l (CCEC, 2007). Moreover, concentration of copper can be change seasonally. Inaba et al,. (1997) found higher concentration of copper in Lake Kasumigaura, Japan during summer and lower concentration of copper in the winter.
Tap and drinking water
Copper found in potable/drinking water in certain concentration. It happens because of contaminate from copper plumbing in the house and corrosion pipes where water to be distributed. Releasing copper will reduce in line with the larger volume of water to flow. In the first flushed of tap water record high concentration of copper. pH, temperature, oxygen, alkalinity, chloride, hardness and availability of copper sources from pipe are responsible to determine concentration of copper in tap water and drinking water (Calle et al., 2007). Mentioned by WHO (2004) that concentration of copper from â‰¤0.005 to â‰¥30 mg/ml belongs to Europe, Canada and USA area and the major source is copper corrosion in pipe water.
Corrosion in the wastewater treatment system cause high amount copper presents in the effluent. Reducing concentration copper in the influent is believed can reduce concentration of copper in the effluent (Isaac et al., 1997). Copper releases to the public sewage systems as results of water discharged from industrial and commercial wastewaters which give contributing more than 40 percent of total, stormwater and surface runoff which reach 30-35 percent of total. The remaining comes from domestic wastewater. Within common wastewater treatment, copper reduce to 80 percent. Therefore, copper contains in public water body is only small portion. Most of copper that released from wastewater treatment is not bioavailable and harmless in the sediments as well as immobilized by binding with organic compounds in the environment (United States Department of Agriculture, 1998).
2.3.4 Guideline and Standard
Pollution Control Department, Ministry of Natural Resources and Environment of Thailand is issued industrial effluent standard and allowable standard for irrigation system which are 2 and 1 mg/l, respectively. Surface water quality standard is set up not more than 0.1 mg/l, while coastal water quality standard is less than 0.005 mg/l. Furthermore, ground water quality standard for Thailand should not exceed 1 mg/l (PCD, 2004).
Copper standard for drinking water is varying among the countries. The summary of copper guidelines in drinking water is listed on Table 2.5
Table 2.5. Allowable standard for drinking water
Source: Fitzgerald, D.J (1998)
2.4. Toxicity and Effects of Copper
Copper is an element which defines as an essential mineral as well as a toxic element. It can be essential nutrient for organism metabolism or gives adverse effects due to its toxicity depend on its range of concentration. There are three zones of critically for copper: deficiency, adequacy and toxicity. Both deficiency and toxicity deliver severe effects from minor to sub clinical symptoms until death in many species (Joseph, 1999). A typical dose-response for copper in human, animals and plants is figured on Figure 2.4. Thus, copper should intake at proper concentration in order to fulfill nutrient needed and to avoid toxicity.
Figure 2.4: A typical dose-response curve for copper in human, animals and plants (Joseph, 1999)
Toxicity of copper to organism especially in the aquatic environment depends on environmental conditions of water such as pH, temperature, turbidity, dissolved oxygen, alkalinity and hardness. Moreover, speciation of copper also influences its toxicity (Rauf and Javed, 2007). Free copper is considered as most toxic species due to its easily reactive by binding with complexes. This form of copper is poisonous especially for lower organisms such as bacteria and other microorganisms (Theophanides & Anastassopoulou, 2002). According to WHO (1970), each of copper salts gives different range of toxic effects. The most toxic of copper salts belongs to copper chloride. However, copper sulphate and copper acetate also vary toxic to organisms. Determination of acute oral toxicity from various copper salts through single oral exposure (Ingestion pathway) is described on Table 2.7.
Organisms can be exposed by copper through some pathways. Drinking water is common pathway which can deliver copper to organisms. Exposure of copper through airborne occurs in the area near smelter and mining activity.
Table 2.7. Toxicity of copper compounds after a single oral exposure (WHO, 1998)
LD50 value (mg/kg body weight)
Equivalent copper dose (mg Cu/kg body weight)
Smyth et al. (1969)
Schafer & Bowles (1985)
Schafer & Bowles (1985)
Copper (II) carbonate hydroxide
Hasegawa et al. (1998)
Copper (II) chloride
Copper (II) hydroxide
Pestice Manual (1991)
Copper (II) nitrate
Smyth et al. (1969)
Copper (I) oxide
Smyth et al. (1969)
Copper (II) oxychloride
Copper (II) sulfate
Smyth et al. (1969)
Venugal & Luckeey (1978)
2.4.1 Effect on Human
Due to copper exposures, some adverse effects are delivered and be harmful to human health. According to ATSDR, effects of copper toxicity covered almost all human organs which are described on Table 2.8
Table 2.8. Effect of copper on human (ATSDR, 2004)
Respiratory irritation, including coughing, sneezing, thoracic pain, and runny nose
Anorexia, nausea and occasional diarrhea
Decreased hemoglobin and erythrocyte levels
Enlargement of the sella turcica, nonsecretive hypophyseal adenoma, accompanied by obesity, arterial hypertension, and "red facies"
Headache, vertigo, and drowsiness
Increasing risk of cancer
Due to central nervous system depression and hepatic and renal failure
Nausea, vomiting, abdominal pain and diarrhea
Risk of coronary heart disease
Risk of coronary heart disease
Depressed skeletal growth
Wilson's disease, Indian childhood cirrhosis, and idiopathic copper toxicosis
Severely burned and debilitated child
Those effects are considered as acute effects and chronic effects. Be acute or chronic are depend on time exposure. An acute effect is effects caused by short time exposure while chronic effects related to long term exposure.
1. Acute effects
Gastrointestinal disturbance indicated by vomiting, burns around epigastrics and diarrhea occurred after ingestion food or drinking water contain copper. Those symptoms are similar to the case of suicidal of copper sulfate during 10 to 60 minute after ingestion. Furthermore, systematic effects will occurs such as delirium, stupor and fail to breathe, and convulsion. Despite of hepatotoxicity effects, hemolysis and hypotension, the worst effect of this toxicity is death. Within 90 minutes after ingestion of copper, cardiovascular falilure and acute renal failure can be occurred (Mortazavi and Javid, 2009).
Acute effects of copper exposure trough drinking water have been examined by Gotteland et al (2001). Symptoms were occurred during permeability test in this experiment are presented on Table 2.8
Table 2.8 Intensity of symptoms from acute copper exposure in conducted permeability test (Gotteland et al, 2001)
Experimental test (10 mg Cu/L)
Feeling of well-being
Paranthesis indicate that number of patients who feel the symptom
2. Chronic effects
Most of chronic effects of copper attacked liver organ. Wilson disease is one of example of chronic effect to make liver as the target of toxicity. Accumulation of copper in the liver, indicated unable of enzyme that responsible to copper transport to excrete it. Eventually, there are excess of copper which spill to blood, brain, kidney and cornea. Cirrhossis hepatic and neurological damage are example of apparent symptoms. Furthermore, wilson disease belong to receives genetic disorder which is called ATP7B gene. Hence, one who carriers this gene will derive the mutation on their children without having the symptoms.
Occupational exposure gives long term exposure due to people often work at metal industry. Copper dust may cause several symptoms such as headache, chili, fever, dryness on mouth and throat and metal fume fever. Workers who exposure to pesticide fumes not only undergo those symptoms but also lung's disease namely vineyard sprayers lung. According to Menezes at al., (2004) workers in galvanizing industry were exposed by copper fume, dust and mist. Copper were found in their toenail, hair and urine.
Ingestion pathway of copper salts trough drinking water delivers gastrointernal disease with nausea symptom. Systemic effects such as damage of hemolysis, liver and kidney are followed due to exposed to copper salts (Ellingsen et al, 2007). By ingesting 0.6-3.8 mg/l of copper in drinking water, pain of abdominal followed by vomiting and diarrhea are occurred (WHO, 1998). At high concentration of copper caused death especially to young children who exposed because of prolonged drinking water consumption.
2.4.2 Effect on Biota
Generally, copper sulphate is recognized as pesticide and herbicide which can contaminate water bodies and eventually up take by aquatic organism. Chen & Lin (2001) mentioned that copper sulphate affects survival, growth and feeding of juvenile Panaeus monodon in concentration 0.45 mg/l and 1 mg/l, respectively.
Rauf and Javed (2007) revealed that water collected from River Ravi, Pakistan and plankton contains was contaminated by copper. Moreover, copper concentration in the water and plankton gives high significant correlation. Phaeodactylum tricornutum defines as marine diatom which can be affected copper toxicity in high concentration. Cid at al., (1994) found 0.1 mg/l of copper was inhibited growth of this alga which is 50 % reduction. Higher concentrations of copper that reach 1 mg/l not only disturb growth but also affected photosynthesis and ATP production.
Copper also brings disturbance embryo and egg of carp. The toxicity of copper delivers abnormal development of embryo, deformation and eventually death of embryo of carp. This condition definitely reduces survival of carp larvae. The experiment was conducted under dechlorinated tap water with temperature 22,2Â°C and pH 7.8 (Åugowska and Witeska). Generally, Responses of aquatic organisms to total dissolved copper in certain ranges are explained in Table 2.6
Table 2.6 Responses expected for various concentration ranges of coppera (WHO, 1998)
Total dissolved Cu concentration range (Âµg/litre)
Effects of high bioavailability in water
Significant effects are expected for diatoms and sensitive invertebrates, notably cladocerans. Effects on fish could be significant in freshwaters with low pH and hardness
Significant effects are expected on various species of microalgae, some species of macroalgae, and a range of invertebrates, including crustaceans, gastropods and sea urchins.
Survival of sensitive fish will be affected and a variety of fish should show sub lethal effects most taxonomic groups of macro algae and invertebrates will be severely affected. Lethal levels for most fish species will be reached
lethal concentrations for the most tolerant organisms are reached
a Sites chosen have moderate to high bioavailability similar to water used in most toxicity tests.
It has been identified that copper give function as trace element for plant to growth. Approximately 8 to 20 ppm copper is needed bt plants. However, presence of copper in high concentration still become problem since this condition causes adverse effects to plant. There are dull of leaf color gradually, chlorisis or necrosis, roof growth disturbance and reduce yields of plants. There was reduction growth of Rhodes grass (Chloris gayana Knuth). The roots of this plant was damage due to expose to copper concentration between 0.2 - 1 ÂµM (Sheldon and Menzies, 2005).
Copper in high concentration also affected microorganism especially on their number and population and diversity. For instance, concentration of copper in surface water which is 0.01 mg/ml will reduce water column bacteria. In addition, bacteria which live in soil will decrease ATP biomass production due to expose to 1000 pg/g copper. Reduction of metabolic activities in line with reducing number of population because their biochemical activity was disturbed by altered environment condition since copper presence at high concentration (Flemming and Trevors, 1989).
2.5. Analytical method for Cu(II) ion
2.5.1 Atomic spectrometric
Copper measurements have been developed rapidly. There are Flame Atomic Absorption Spectrophotometry (FAAS), Electrothermal atomic absorption spectrophotometry (ETAAS), Inductively coupled Plasma Optical emission spectrophotometry (ICP-OES), and inductively coupled mass spectrophotometry (ICP-MS) for copper determination in biological samples and water samples (Ellingsen et al., 2007). Analytical methods for copper detection in the fresh water samples are listed in Table 2.9.
Table 2.9. Common analytical methods of detection copper in the fresh water samples (WHO, 1998)