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Chapter 1

Introduction

Background

Bing an indispensable hint component, Cu ( Cu ) is ever involved for many biological procedures because its ain of import function for catalytic cofactor in oxidative enzymes ( Puig and Thiele, 2002 ) . Therefore, Cu is needed by beings to work their metamorphosiss at sufficient concentration. Harmonizing to WHO ( 1998 ) day-to-day demands of Cu for homo is 1.2 – 1.3 milligram Cu/day for both big adult females and work forces. However, lack and surplus of Cu causes toxicity for beings. Several inauspicious effects have been delivered to human and other being every bit good as environment. Exposure of Cu on homo will do accretion in their GI, liver, kidney, encephalon and besides eyes ( WHO, 2004 ) . In add-on, Menkes syndrome, Wilson disease and Indian Childhood Cirrhosys are determined as familial upsets related to metamorphosis of Cu.

In environmental system, Cu can be present in dirt, air and H2O organic structure. Although presence of Cu originate from natural beginnings which are caused by precipitation and weathering procedures, anthropogenetic beginnings declare as chiefly beginnings of Cu. Naturally, Cu nowadays in aquatic system in low concentration. Since part of industry discharged and sewage intervention workss, agribusiness and excavation activities make copiousness of Cu in the aquatic environment at the high concentration. This status makes Cu classified as common pollutant in H2O organic structure. Harmonizing to Calle et Al ( 2007 ) corrosion of plumbing makes highly handiness of Cu in imbibing H2O whereas US EPA has been set up criterion of allowable Cu in imbibing H2O non more than 1.3 mg/l.

Assorted concentration of Cu and its bioavailability in the aquatic environment related to several factors such as H2O hardness, pH, organic ligands, suspended particulate affair and carbonates through complexation, precipitation and surface assimilation. Copper which release to the aquatic system occurs in signifier of free ionic cupric cation ( Cu2+ ) and soluble composites. In province of Cu ( II ) ion, Cu signifiers coordination compounds or composites with both inorganic and organic ligands. Its signifier becomes of import oxidization province of Cu in natural aquatic environments due to its extremely reactive feature. Therefore, Cu ( II ) ion is classified as most toxic species in the aquatic environment.

Presently, there are several methods which develop to observe Cu ( II ) ion due to non merely its environmental importance but besides being as toxic component. GFAAS, ICP-MS and ICP-OES are considered as the common methods for hint 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 every bit good as its strength determine feature of each component and its concentration. Alternatively of measuring of an component, ICP-MS and ICP OES capable to observe multi component and their concentrations at the same time at high and sub ppb sensing bound ( Perkinelmer, 2009 ) . Unfortunately, these methods are classified as expensive methods because of utilizing extremely technological instruments and complicated method to run the instruments.

Therefore, a chemosensor has been introduced to get the better of restrictions from others methods in analysis of Cu ( II ) ion. A chemosensor is a chemical detector that detects and recognizes the analytes and changes its physical belongings upon interaction between detector and analytes. The changing of physical belongings involves colour alterations every bit good as fluorescent emanation of the detector which can be detected easy. A chemosensor which introduces colour altering during reaction procedure is called colorimetric chemosensor. Another detector which induces fluorescent alterations has been known as fluorogenic chemosensor.

Unlike fluorogenic chemosensors which are required the instruments to observe fluorescent emanation, colorimetric chemosensors offer effortless sensing method ( Lu, 2009 ) . Naked oculus can be signaled whether any presence of hint elements including Cu ( II ) ion due to colourise altering. Therefore, there is progressively demand to develop many researches sing to colorimetric detector. Of many researches have been conducted, Pyrazolidine Luminol ( PL ) is found as a colorimetric chemosensor. This detector has been identified as a selective detector for Cu ( II ) ion. Using this detector, the presence of Cu ( II ) in aqueous can be detected straight by bare oculus. Upon adhering between the detector and Cu ( II ) ion, it induces the alteration of colour from pale xanthous to dark green.

A survey about Pyrazolidine Luminol ( PL ) as a colorimetric chemosensor for Cu ( II ) ion sensing in term of environmental application is focused. The purpose of this survey is to develop a colorimetric chemosensor for the sensing Cu ( II ) ion contaminated in H2O and effluent. Detection bound of this detector is of import to specify. For applicable intent, the detector strip is designed by coated pyrazolidine luminol over the silica home base. The binding between Pyrazolidine Luminol and Cu ( II ) ion on silicon oxide home base will bring on the alteration of the colour. This survey is expected to make a new detector for Cu ( II ) ion based on Pyrazolidine Luminol for sensitive and selective sensing of Cu ( II ) ion contaminated H2O.

1.2 Statement of jobs

Copper as a hint component is present in the environment. Soil, deposit, saltwater, land H2O, surface H2O and imbibing H2O contain sum of Cu at assorted concentration. Presence of Cu can be over allowable criterion which had set up by authorities or organisation such as WHO and US EPA. This status occurred because other beginnings generated Cu in high sum. For case, electroplating, pigment and electronic industries generated effluents which have high Cu. Particularly in the aquatic environment, Cu was available in soluble signifier. In this signifier, Cu was taken up by animate beings, works, algae and bacteriums signifier, and so give harmful consequence to them. For case, Cu sulfate used to use as algae control in the lake. Furthermore, It was a great concern to acknowledge concentration of Cu in the environment particularly in aquatic environment due to its toxicity to environment every bit good as to human wellness.

Recently, engineerings have been completed to observe hint component including Cu. These instruments belong to high engineering devices. They can be detected concentration of Cu up to 0.01 Aµg/l in H2O sample ( WHO, 1998 ) . However, accomplishments and cognition are needed to run those instruments. Not merely high cost but besides proper sample readyings 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 Cu for step the H2O sample. Mistake within fixing concentration of standard curve influenced the consequences of measuring. Other mistakes of measuring used to take topographic point during the procedure because of improper cares instrument and besides human mistake. Due to completed processs, non many people capable to utilize those instruments.

Some researches have been synthesized colorimetric chemosensor for Cu ( II ) ion dectection as a alternate method. Azobenzene-based receptors examined as Cu ( II ) ion selective colorimetric chemosensor that give a alteration colour from ruddy to blanch xanthous ( Lee et all. , 2007 ) . Furthermore, synthesized of rhodamine derivative by Chen et al. , ( 2009 ) proposed Cu ( II ) ion colorimetric chemosensor from colorless to a ruddy colour. However, a colorimetric chemosensor which can be addressed to application in H2O and effluent sample is imperative to realize due to non all of colorimetric chemosensors can be transformed into chemosensor strips. Choice of solid support, exact concentration of detector to be coated on it and dependance of environmental parametric quantities are some factor that affect a chemosensor strip to be effectual apply in H2O and effluent sample ( Diez-Gil EL al. , 2007 ; Capitan-Valley et al. , 2003 )

Finally, PL detector are found as a colorimetric chemosensor which able to alter its colour from pale xanthous 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 instead device to observe presence of Cu in the aqueous environment. By coated on silice home base, this detector is expected to catch up for field work application. It has been attempted that this device can derive its high sensing bound. To observe concentration of Cu in H2O and effluent, it is of import to make device which sensitive, can be use easy and applicable in the field survey.

1.3 Aims of the survey

The aim of the survey is to make chemosensor strips for Cu ( II ) ion presence in H2O and effluent sample.

The specific aims are

To develop a PL strip for the sensing of Cu ( II ) ion in aqueous environment

To find the sensing bound of PL strip

To use the PL strip for the sensing of hint sum of Cu ( II ) ion in aqueous environment compared with the known methods, e.g. ICP-OES

1.4 Scope of the survey

The range of survey is to develop new chemosensor for the sensing of Cu ( II ) ion in an aqueous environment. Due to limited clip, this survey will concentrate to develop PL sensing bound in order to accomplish its highest value. The undertaking will get down from the synthesis of PL. The selectivity of the detector for Cu ( II ) ion over other metals will be investigated. The sensing bound of PL detector are determined in the research lab by usage known concentration of Cu ( II ) ion solution. 1HNMR trial and UV spectrometric analysis will clarify the binding mechanism. Coating technique on silicon oxide home base will be used to develop a detector strip. The samples of H2O and effluent which contain Cu ( II ) ion will be measured utilizing the detector strips. Finally, the comparing with another method is perfectly needed to guarantee the efficiency of the detector strips. Intensity of colour altering reflects the concentration of Cu ( II ) ion detected by the detector.

Chapter 2

Literature Review

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, Cu become the 29th component which classify as passage metal. Copper owns its atomic weight of 63.546, denseness of 8.9, and runing point of 1083.4A°C. Copper gives bright metallic looking with soft and easy to organize. Furthermore, the electronic constellation of Cu is 1s2 2s2 2p6 3s2 3p6 4s1 3d10 which cause a partly filled vitamin D subshell. Consequently, Cu delivers tendency to organize complex ions and occurs oxidization provinces ( Nriagu, 1979 ) .

Naturally, Cu compounds present in the 0, I, II, and III oxidization provinces. Most of Cu ( I ) ion are oxidized easy to Cu ( II ) ion while Cu ( III ) ion merely found in few compounds due to troubles of oxidization in this province. Furthermore, Cu ( II ) ion plays function as of import oxidization province in the aqueous environment trough become powerful oxidizing agent. The Cu ( II ) ion shows readily distortion passage belongingss such as colour, signifier of complexed and paramagnetism. Preferentially Cu ( II ) ion binds with both organic and inorganic ligands which cause Cu in the natural samples are largely complexed with organic compounds. These compounds are soluble in H2O. Dissolution of Cu ( II ) ion besides occurs in the hydrated oxide, carbonate and acid which give blue green colour ( Wilson & A ; Newall, 1970 ; Cotton & A ; Wilkinson, 1989 ; WHO, 1998 ) .

Besides found in the assortment of minerals, Cu becomes major constituent of common stones. Copper is dispersed widely in signifier of minerals such as sulphides, arsenides, chlorides and carbonates. The illustrations of common Cu minerals salts are bornite ( Cu5FeS4 ) and chalcopyrite ( CuFeS2 ) . Chalcopyrite is most copiousness due to widely distributed in stones and concentrated in the largest Cu ore sedimentation. In add-on, Cu Acts of the Apostless as rocks- forming minerals which make pyrogenic stones from its hint sums in silicon oxide minerals ( Nriagu, 1979 ; Adriano, 1986 ) . The sum-up of physical chemical belongingss of Cu and some of its salts are presented in Table 2.1

Table 2.1 Physical and chemical belongingss of Cu and its salts

Copper

Copper ( II ) sulphate

Cuprous ( I )

Oxide

Copper ( II )

hydrated oxide

Copper ( II )

Chloride

CAS register figure

Molecular expression

Relative molecular mass

Boiling point ( A°C )

Melting point ( A°C )

Vapour force per unit area

( kPa )

Water solubility

7440-50-8

Copper

63.55

2567

1083.4

1.33 at 1870 A°C

indissoluble

7758-98-7

CuSO4

159.6

decomposes at 650 A°C

decomposes at & gt ; 200A°C

143 g/litre at 0A°C

1317-39-1

Cu2O

141.3

1235

indissoluble

20427-59-2

Cu ( OH ) 2

97.56

decomposes at 140 A°C

decompose

2.9 g/litre

at 25 A°C

7447-39-4

CuCl2

134.45

decomposes at 993 A°C

620

706 g/litre

Beginning: Like & A ; Frederikse ( 1993 )

2.2 Copper Uses

Belong to third ranking of universe metal ingestion, Cu ain high demand progressively. During 1900 to 2000, Cu ingestion has reached lifting demand up to 13 1000000s tones. It will be predicted that Cu demand maintain to follow progressively tendency peculiarly in the development states which concentrate on industrialisation. Most of Cu is used as electrical merchandises such as overseas telegram wire since its features as an first-class music director. Durable corrosion makes Cu to go common plummeting stuff. Copper is besides determined as extra ingredient in many valuable metals. In a line with development of engineering, Cu is utilized in modern transit and electronics. For case, there were 40 lbs of Cu in United Stated of luxury car ( CDA, 2010 ) . Harmonizing to Kelly & A ; Matos ( 2005 ) in US Geological Survey, end utilizations of Cu are divided into five major groups ; constructing buildings, electrical and electronics merchandises, industrial machinery and equipment, transit equipment and costumier general merchandises. The figure of Cu ingestion each group in the United Stated is explained on Figure 2.1.

Figure 2.1: Copper uses in Unites States ( Kelly & A ; Matos, 2005 )

In agribusiness Fieldss, Cu in signifier of Cu sulfate have been functioned as antifungal or algaecide. This compound is able to forestall fungi-based diseased on works every bit good as to suppress putrefactions on parts of workss. Impact of water-borne diseases can be reduced by adding Cu into H2O. Water reservoirs besides used to hold Cu in order to command algae growing. In add-on, Cu compounds have been employed many old ages to kill parasites in freshwater aquaculture farms and pools ( CDA, 2010 ) . Therefore, Cu is recognized widely in many Fieldss of application.

2.3 Copper in the environment

2.3.1 Beginnings and Origin

Copper which released to the environment comes chiefly from two beginnings: natural beginnings and anthropogenetic beginnings. In natural beginnings, together with other minerals, Cu takes portion in organizing Earth ‘s crust which derived from its parent stuffs. In these stuffs, Cu undergoes enduring procedure that becomes natural beginnings of Cu in the dirt. Precipitation, deposition and resulting of deposit sedimentation besides allow Cu to be distributed in the environment. In the atmospheric, Cu emit into environment due to windblown dust, wood fire, vents atoms, flora, seasalt sprays, and stone degassing. Appraisal of natural beginnings emanation of Cu in the ambiance are windblown dusts, 0.9-15 A- 103 metric tons ; forest fires, 0.1-7.5 A- 103 metric tons ; volcanic atoms, 0.9-18 A- 103 metric tons ; biogenic procedures, 0.1-6.4 A- 103 metric tons ; sea salt spray, 0.2-6.9 A- 103 metric tons severally ( Nriagu, 1979 ) . Furthermore, dead being can be defined as important natural beginnings of Cu in the marine ecosystem ( WHO, 1998 ) .

Anthropogenetic beginnings give higher part for the presence of Cu in the air, dirt and aquatic environment. Copper processing operation, baccy fume, burning of coal in the power works are defined as beginnings of Cu emanation to the ambiance. These beginnings are about three times higher than copper flux from natural beginnings. For case, per centums of Cu emanation from anthropogenetic beginnings are 7.4 % from Fe and steel production. Followed by 4.6 % , 3.3 % , 2.7 % , and 1.9 % from coal and oil burning, Zn smelting, Cu sulphate production, municipal incineration, severally. From other beginnings contribute 2.3 % ( Lide and Frederikse, 1993 ) .

Nriagu ( 1979 ) declares chief anthropogenetic beginnings of Cu in the dirt are as follows:

Mining and smelting activities

Industrial wastewater and traffic

Urban development and dumped waste stuffs

Dust and rainfall

Sewage sludge, hog slurry and composted garbage

Fertilizer, ameliorants and pesticides

In the aquatic environment, by and large Cu is classified as nonpoint beginning which is come from anthropogenetic beginnings. For case, urban overflow, agricultural overflow, and yachting activity are common beginnings of Cu in standard H2O ( BSDC, 2003 ) . Likewise Joseph ( 1999 ) the presence of Cu is caused by H2O and waste discharge, rain H2O overflow, and air-borne dust. Antifouling marine pigment is besides declared as a manner to released Cu in the marine ecosystem. In add-on, urban stormwater overflow besides contains Cu. Davis et Al ( 2001 ) have estimated Cu lading from assorted beginnings in urban stormwater which is 0.324 kg/ha-yr. Appraisal of assorted beginnings of Cu in the urban stormwater overflow is presented on Figure 2.1.

Figure 2.1: Assorted beginnings of Cu in the urban stormwater overflow ( Davis et al. , 2001 )

TBC Environmental study ( 2004 ) listed anthropogenetic beginning contribute to South San Francisco Bay which can be represented of listed Cu beginning in the coastal environment. Normally, they release from shoreline activities every bit good as urban overflow. Assorted Cu beginnings and primary Cu beginning which release to the coastal environment are explained in Table 2.2

Table 2.2 Copper beginning listed

Copper beginnings

Primary Cu beginnings

Air deposition Conveys Cu from many beginnings

Conveys copper from many beginnings

Car dismantlers ( overflow )

Vehicle parts

Brake tablets

Brake tablets

Commercial and residential land utilizations

( overflow )

Conveys copper from many beginnings

Construction activities-copper in sand

blaring scoria and Cu

Copper in waste stuffs used for surface coatings sandblasting, Cu architectural

stuffs

Copper algaecides ( swimming pools, watering place,

fountains, and cosmetic pools )

Copper algaecides

Copper algaecides in H2O supply systems

and reservoirs

Copper algaecides

Copper antifungals and weedkillers

Copper-containing pesticides

Copper in imported H2O supply

Copper in beginning H2O, Cu

algaecides

Gas Stations

Brake tablets, other vehicle beginnings

Highway overflow

Conveys copper from many beginnings

Illicit connexions

Copper in effluent ( conveys Cu

from many beginnings )

Industrial land usage

Conveys copper from many beginnings

Landfills

Conveys copper from many beginnings

Open infinite

Dirt

Parking tonss and care paces ( overflow )

Conveys copper from many beginnings

Spills and illegal dumping ( copper taint in motor oil, Cu containing

pesticides )

Many Cu beginnings

Street overflow

Conveys copper from many beginnings

Tap H2O

Copper pipes, Cu in beginning H2O, Cu algaecides

Vehicle Fuels ( Exhaust )

Vehicle fuels

Wastewater intervention workss

Copper in effluent ( conveys Cu from many beginnings )

Beginning: TDC Environmental

2.3.2 Fate and Behavior

Copper may show in the natural Waterss, effluent, and industrial waste watercourse every bit good as in portable H2O. In aqueous environment, Cu found in several signifiers such as indissoluble, free dissolved, complexed dissolved and entire recoverable. For illustration indissoluble Cu is known as Cu sulphides and hydrated oxides ( Gibbs, 1994 ) .

Since Cu releases to the aqueous environment, its handiness, mobility and species signifiers will change because of complexation procedure. Free cuprous cation ( Cu2+ ) created due to it associates with H2O. It will adhere with inorganic ligands, largely the hydroxyl ( OH- ) and carbonate ions ( CO32- ) . Therefore, H2O hardness drama of import function in this procedure. High of H2O hardness makes the more capacity of Cu complexing. As the consequence, toxicity of Cu goes down in line with increasing of H2O hardness. Stronger adhering Cu with organic compound occurs in ligands which have electron giver of O, N and S ( Flemming and Trevors, 1989 ) . These binding will transform Cu speciation in aqueous environment. Furthermore, pH besides influences on Cu speciation. Harmonizing to Hong et al. , ( 2010 ) , soluble Cu concentration is decrease half at pH 7.5. However, precipitated Cu will be formed as increasing of pH. Entire Cu will stay stable in broad scope of pH. Impact of pH on entire Cu, soluble Cu and precipitated Cu on Cu speciation in a chemical-equilibrium theoretical account is presented in Figure 2.2.

Figure 2.2: Impact of pH on entire Cu, soluble Cu and precipitated Cu ( Lin et al. , 2002 )

As mentioned by Flemming and Trevors ( 1989 ) precipitation and surface assimilation procedures play important function to find species and concentration of Cu. Those procedures declare as tracts to cut down concentration of Cu in H2O column. The soluble Cu corsets in H2O column. Together with atom in suspension, Cu will precipitate into deposit. Role of organic affair, oxides of Fe, manganese and aluminium, interaction with other elements as Cu adsorbent give great part to impact mobility and handiness of Cu in the environment ( Adriano, 1986 ) . Both inorganic deposits and organic deposit contain sum of Cu which are vary in concentration and species. Copper-organic affair binding is abundance in organic deposit while cupric salt is formed in inorganic deposit ( ATSDR, 2004 ) . Furthermore, vary oxidization province of Cu in the H2O and deposit influences bioaccumulation Cu on the biology of the H2O system.

Precipitation of Cu in the dirt occurs readily within alkalic status. Furthermore, acerb status non merely gives enhancement degree of ionic Cu but besides maintains solubility of Cu. At pH 2.8, Cu undergo considerable mobilisation merely with drawn-out leaching. Copper which presence in the top centimetre of acerb dirt is easy to do organic bounding, 18 % of Cu stay in hydroxyl carbonate edge, 7 % was surface assimilation, followed by 11 % edge with other ions, 6 % irreversibly adsorbed. At pH 4.5 sum of extractible is 3 % and eventually merely 3 % Cu stay mobile ( Lide, 1997 ) .

Cycling of Cu involves several procedures such as mobilisation or conveyance, distribution and transmutation which affect bioavailability and bioaccumulation of Cu in the environment. Copper is released to atmospheric, aquatic and land ecosystem from both its natural and anthropogenetic beginnings. Emission of Cu to air environment occurs in particulate affair signifier or absorbed into particulate affair. Distance of going particulate affair in the air depends on beginnings of Cu emanation, its size, wind speed and turbulency. In the atmospheric, gravitative subsiding, dry and wet deposition make Cu to be removed ( ATSDR, 2004 ) . However, Cu in the dirt undergoes deposition. Not merely organic affair but besides C minerals and clay adsorb Cu presence in the dirt. Copper which is released to the aquatic environment is carried out to the H2O column and deposits by settle down, precipitate and adsorb procedures ( WHO, 1998 ) . Cycling of Cu in the environment is described briefly trough Figure 2.3.

Copper in

land biology

Copper in fresh water

Ecosystem

Cu sedimentation

Fossil Fluels

Cu in dirt

Copper in groundwater

particulate

soluble

Volcanic emanation

Organic particulate

Anthropogenetic emanation

Atmospheric deposition

Fertilizer and waste disposal

River run-off

Windblown dust

Seasalt spray

Atmospheric deposition

Dissolved Cu

Copper in Marine

biology

Cu in deposits

Cu in pore H2O

precipitation

Deep entombment

outflux

Deposition

Decomposition

consumption

Water discharges

Figure 2.3: Copper rhythm in the environment

2.3.3 Environmental degrees

Air

Average background concentrations of Cu in air in rural countries range from 5 to 50 ng/m3 while concentration in the urban ranges below 1 Aµg/l. Beginnings of Cu which are released to the ambiance becomes major factors of degree Cu in the air. Approximately 0.036 ng/m3 Cu found in the air of South Pole ( Ellingsen et al. , 2007 ) . ATSDR ( 2004 ) reveals copper degree in the air environment from 1 up to 200 ng/m3. This scope becomes higher that range 5000 ng/m3 in the smelters and environing of Cu excavation country.

Seawater

In the coastal and estuaries, Cu occurs in higher degree than saltwater. Copper found in the uncontaminated saltwater with concentration less than 1 Aµg/l. Copper shows increasing of concentration in the near of surface saltwater ( less than 200 m ) and steady addition in the down of seafloor ( WHO, 1998 ) . Concentration of Cu in Marine, oceans and estuarine of the several parts is listed on Table 2.3.

Table 2.3. Copper concentration in Marine and estuarial H2O ( Joseph, 1999 )

Location

Scope

Location

Scope

North Sea and Baltic Sea Region

Baltic Sea

Northern Baltic Sea

ASV-labile

ASV-total

Gotland Deep

Klaypeda Inlet

Vassorfarden Bay, Findland

Kirsiu Marios Lagoon, Lithuania

North Sea

Framwaren Fjord, Norway

Schelidi Estuary, Belgium

Firth of Fourth, Scotland

D ( 189,361 ) ng/L

D ( 379,537 ) ng/L

D ( 0.05-0.72 ) Aµg/L

D ( 2.4 – 9.2 ) Aµg/L

69 Aµg/L

0.004-0.016 mg/L

T ( 0.13-5.00 ) nanometer

D ( 0.84-2.6 ) Aµg/L

D ( 1.05-2.59 ) Aµg/L

East and India Ocean Region

Mekong river Coast

Saigon River Station

Qiantang-jiang Estuary

Erhjen Chi, Taiwan

River H2O

Mariculture H2O

Takasaki Seto, Japan

Surface saltwater

Bottom saltwater

Uranouchi Bay, Japan

Surface saltwater

Bottom saltwater

Boso Peninsula

Surface saltwater

Bottom saltwater

D ( 1.2-17.1 ) Aµg/L

D ( 1.4-9.6 ) Aµg/L

T ( 17.20-26 ) Aµg/L

56.61-793.50 ppb

5.53-86.88 ppb

0.39-0.99 Aµg/L

0.42-0.70 Aµg/L

0.38 Aµg/L

0.87 Aµg/L

0.20-0.34 Aµg/L

1.24 Aµg/L

North Atlantic Ocean Region

Lavos Region, Portugal

Sargasso Sea

Deep sea

Surface transects

United States of America

Pettaquamseun Estuary, RI

Mississippi River Delta, LA

Vero Beach, FL

North Contentin, France

D ( ND-10.7 ) Aµg/L

T ( 0.79-2.2 ) nanometer

T ( 0.09-3.3 ) nanometer

D ( 0.13-0.53 ) Aµg/L

D ( 18.3-23.8 ) nmol/kg

D ( 100 ) ng/L

D ( 0.13-0.8 ) Aµg/L

T ( 0.25-1.20 ) Aµg/L

South-polar Ocean Indian Section

India

Arabian Sea

Purna River Estuary

Lakshoaweep Lagoon

Inside laguna

Outside laguna

Mindhola River Estuary

North Pacific Region

USSR, Gulf of Peter the Great

Northeast Pacific-Deep Sea

D ( 0.28-4.05 ) Aµg/L

D ( 5.73-8.00 ) Aµg/L

D ( 3.8-7.6 ) Aµg/L

D ( 0.69-4.68 ) Aµg/L

D ( 0.96-3.27 ) Aµg/L

D ( 2.7-15.9 ) Aµg/L

0.70-1.90 Aµg/L

T ( 1.6-3.9 ) nanometer

South Atlantic Region

Argentina

Blanca Bay

Embudo Channel

Bermejo Channel

Falsa Bay

Verde Bay

South Atlantic

South-polar Ocean

South Shetland Islands, Antarctic

D ( 1.7-3.3 ) Aµg/L

T ( 1.7-3.3 ) Aµg/L

D ( 6.80 ) Aµg/L

D ( 5.30 ) Aµg/L

D ( 4.70 ) Aµg/L

D ( 4.20 ) Aµg/L

D ( 0.8-2.3 ) Aµg/L

D ( 0.7-2.2 ) Aµg/L

2.3 Aµg/L

United States of America

Santa Monica Basin,

Surface Ellion Bay

Commencement Bay

T ( 1.4-3.0 ) nanometer

D ( 3.38-259.34 ) Aµg/L

T ( 9.57-3215.34 ) Aµg/L

D ( 2.91-45.72 ) Aµg/L

T ( 3.85-631.72 ) Aµg/L

Thymine: Entire Cu, D: Dissolve Cu

Dirt

In the Earth ‘s crust, concentration of Cu varies from 24 to 55 ppm. For uncontaminated dirt, its average concentration reaches 30 milligram Cu/kg and falls in the scope 2 – 350 mg/kg ( WHO, 1998 ) . Vary concentration of Cu in dirt depend on its parent stuff feature and distance from anthropogenetic beginnings, dirt type and amendment. For case, concentration Cu in dirt near smelters and excavation can accomplish to 17000 ppm. Concentration of Cu in Canadian dirt falls in the scope 2- 100 mg/kg with mean 20mg/kg ( ATSDR, 2004 ) .

Sediment

For uncontaminated deposits found concentration of background Cu between 800 to 5000 mg/kg. Copper degrees in Marine deposits range from 2 to 740 mg/kg ( dry weight ) ( WHO, 1998 ) . Summary of Cu concentration in assorted deposits is formulated on Table 2.4.

Table 2.4 Copper concentrations in deposits

Sediments

Unit of measurement

Concentration

Coastal

Particulate

Interstitial H2O

ppm

ppb

0.03-3,789

25.5-32.7

Estuarine

Particulate

Interstitial H2O

ppm

ppb

0.3-2,985

0.3-100

Ocean

Particulate

Interstitial H2O

ppb

ppm

3.1-648

22-45

Lake

Particulate

Interstitial H2O

ppm

ppb

0.4-796

45.6-52

River

Particulate

ppm

5.3-4,570

Beginning: ATSDR ( 2004 )

Surface H2O

Approximately 1-10 Aµg/l of concentration Cu occur in the lake and river with mean 4 Aµg/l ( WHO, 1998 ) . Sum of Cu in ambient Canadian surface H2O found 0.005 mg/l ( CCEC, 2007 ) . Furthermore, concentration of Cu can be change seasonally. Inaba et Al, . ( 1997 ) found higher concentration of Cu in Lake Kasumigaura, Japan during summer and lower concentration of Cu in the winter.

Tap and imbibing H2O

Copper found in potable/drinking H2O in certain concentration. It happens because of contaminate from Cu plumbing in the house and corrosion pipes where H2O to be distributed. Let go ofing Cu will cut down in line with the larger volume of H2O to flux. In the first flushed of tap H2O record high concentration of Cu. pH, temperature, O, alkalinity, chloride, hardness and handiness of Cu beginnings from pipe are responsible to find concentration of Cu in tap H2O and imbibing H2O ( Calle et al. , 2007 ) . Mentioned by WHO ( 2004 ) that concentration of Cu from a‰¤0.005 to a‰?30 mg/ml belongs to Europe, Canada and USA country and the major beginning is copper corrosion in pipe H2O.

Effluent

Corrosion in the effluent intervention system cause high sum Cu nowadayss in the wastewater. Reducing concentration Cu in the influent is believed can cut down concentration of Cu in the wastewater ( Isaac et al. , 1997 ) . Copper releases to the public sewerage systems as consequences of H2O discharged from industrial and commercial effluents which give lending more than 40 per centum of entire, stormwater and surface overflow which reach 30-35 per centum of entire. The staying comes from domestic effluent. Within common effluent intervention, Cu cut down to 80 per centum. Therefore, Cu contains in public H2O organic structure is merely little part. Most of Cu that released from effluent intervention is non bioavailable and harmless in the deposits every bit good as immobilized by adhering 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 outflowing criterion and allowable criterion for irrigation system which are 2 and 1 mg/l, severally. Surface H2O quality criterion is set up non more than 0.1 mg/l, while coastal H2O quality criterion is less than 0.005 mg/l. Furthermore, land H2O quality criterion for Thailand should non transcend 1 mg/l ( PCD, 2004 ) .

Copper criterion for imbibing H2O is changing among the states. The sum-up of Cu guidelines in imbibing H2O is listed on Table 2.5

Table 2.5. Allowable criterion for imbibing H2O

Unit of measurement

Concentration

Health-based

US EPA

Australia

WHO

mg/l

1.3

2.0

2.0

Aesthetics-based guideline

WHO

European Commission

Australia

US EPA

mg/l

1.0

3.0

1.0

1.0

Beginning: Fitzgerald, D.J ( 1998 )

2.4. Toxicity and Effectss of Copper

Copper is an component which defines as an indispensable mineral every bit good as a toxic component. It can be indispensable food for being metamorphosis or gives inauspicious effects due to its toxicity depend on its scope of concentration. There are three zones of critically for Cu: lack, adequateness and toxicity. Both lack and toxicity deliver terrible effects from minor to stand in clinical symptoms until decease in many species ( Joseph, 1999 ) . A typical dose-response for Cu in human, animate beings and workss is figured on Figure 2.4. Therefore, Cu should intake at proper concentration in order to carry through food needed and to avoid toxicity.

Figure 2.4: A typical dose-response curve for Cu in human, animate beings and workss ( Joseph, 1999 )

Toxicity of Cu to organism particularly in the aquatic environment depends on environmental conditions of H2O such as pH, temperature, turbidness, dissolved O, alkalinity and hardness. Furthermore, speciation of Cu besides influences its toxicity ( Rauf and Javed, 2007 ) . Free Cu is considered as most toxic species due to its easy reactive by adhering with composites. This signifier of Cu is toxicant particularly for lower beings such as bacteriums and other micro-organisms ( Theophanides & A ; Anastassopoulou, 2002 ) . Harmonizing to WHO ( 1970 ) , each of Cu salts gives different scope of toxic effects. The most toxic of Cu salts belongs to copper chloride. However, Cu sulfate and Cu ethanoate besides vary toxic to organisms. Determination of acute unwritten toxicity from assorted Cu salts through individual unwritten exposure ( Ingestion pathway ) is described on Table 2.7.

Organisms can be exposed by Cu through some tracts. Drinking H2O is common tract which can present Cu to organisms. Exposure of Cu through airborne occurs in the country near smelter and excavation activity.

Table 2.7. Toxicity of Cu compounds after a individual unwritten exposure ( WHO, 1998 )

Salt

Speciess

LD50 value ( mg/kg organic structure weight )

Equivalent Cu dosage ( mg Cu/kg organic structure weight )

Mentions

Copper ( II ) ethanoate

rat

rat

mouse

595

710a

1600a

( deadly dosage )

208

226

509

NIOSH ( 1993 )

Smyth et Al. ( 1969 )

Schafer & A ; Bowles ( 1985 )

Copper ( II ) carbonat

rat

mouse

159

320

( deadly dosage )

82

165

Lehman ( 1951 )

Schafer & A ; Bowles ( 1985 )

Copper ( II ) carbonate hydrated oxide

rat ( male )

Rat ( female )

coney

1350

1495

317

388

430

91

Hasegawa et Al. ( 1998 )

NIPHEP ( 1989 )

Copper ( II ) chloride

Rat

Mouse

Guinea-pig

150

190

32

66

90

15

Lehman ( 1951 )

NIPHEP ( 1989 )

NIPHEP ( 1989 )

Copper ( II ) hydrated oxide

rat

1000

651

Pestice Manual ( 1991 )

Copper ( II ) nitrate

rat

940b

247

Smyth et Al. ( 1969 )

Copper ( I ) oxide

rat

470

417

Smyth et Al. ( 1969 )

Copper ( II ) oxychloride

rat

rat

700-800

1440

417-476

857

Tomlin ( 1994 )

NIEHP ( 1989 )

Copper ( II ) sulphate

rat

rat

mouse

300

960c

50 ( LD100 )

120

244

20

Lehman ( 1951 )

Smyth et Al. ( 1969 )

Venugal & A ; Luckeey ( 1978 )

a Monohydrate

B Trihydrate

degree Celsiuss Pentahydrate

2.4.1 Effect on Human

Due to Cu exposures, some inauspicious effects are delivered and be harmful to human wellness. Harmonizing to ATSDR, effects of Cu toxicity covered about all human variety meats which are described on Table 2.8

Table 2.8. Consequence of Cu on homo ( ATSDR, 2004 )

Nerve pathway

Consequence

Sympthom

Inhalation

Systemic Effectss

Respiratory annoyance, including coughing, sneezing, thoracic hurting, and runny nose

Gastrointestinal Effectss

Anorexia, sickness and occasional diarrhoea

Hematologic Effectss

Decreased haemoglobin and red blood cell degrees

Hormone Effectss

Expansion of the sella turcica, nonsecretive hypophyseal adenoma, accompanied by fleshiness, arterial high blood pressure, and “ ruddy facies ”

Ocular Effectss

Eye annoyance

Neurological Effectss

Headache, dizziness, and sleepiness

Generative Effectss

Sexual powerlessness

Cancer

Increasing hazard of malignant neoplastic disease

Oral

Death

Due to cardinal nervous system depression and hepatic and nephritic failure

Gastrointestinal Effectss

Nausea, purging, abdominal hurting and diarrhoea

Cardiovascular Effectss

Hazard of coronary bosom disease

Hematologic Effectss

Hazard of coronary bosom disease

Musculoskeletal Effectss.

Depressed skeletal growing

Hepatic Effectss

Wilson ‘s disease, Indian childhood cirrhosis, and idiopathic Cu toxicosis

Dermal

Hematologic Effectss

Badly burned and debilitated kid

Ocular Effectss

Eye annoyance

Those effects are considered as acute effects and chronic effects. Be acute or chronic are depend on clip exposure. An acute consequence is effects caused by short clip exposure while chronic effects related to long term exposure.

1. Acute effects

Gastrointestinal perturbation indicated by purging, Burnss around epigastrics and diarrhoea occurred after consumption nutrient or imbibing H2O contain Cu. Those symptoms are similar to the instance of suicidal of Cu sulphate during 10 to 60 minute after consumption. Furthermore, systematic effects will happen such as craze, daze and neglect to take a breath, and paroxysm. Despite of hepatotoxicity effects, haemolysis and hypotension, the worst consequence of this toxicity is decease. Within 90 proceedingss after consumption of Cu, cardiovascular falilure and acute nephritic failure can be occurred ( Mortazavi and Javid, 2009 ) .

Acute effects of Cu exposure trough imbibing H2O have been examined by Gotteland et Al ( 2001 ) . Symptoms were occurred during permeableness trial in this experiment are presented on Table 2.8

Table 2.8 Intensity of symptoms from acute Cu exposure in conducted permeableness trial ( Gotteland et al, 2001 )

Symptom

Experimental trial ( 10 mg Cu/L )

Results

Nausea

Vomiting

Abdominal hurting

Diarrhea

Entire

13 ( 6 )

4 ( 2 )

3 ( 3 )

0

20 ( 7 )

Distracters

Backache

Feeling of wellbeing

Concern

Cough

Dizziness

Palpitations

Fatigue

Entire

0

0

4 ( 4 )

0

0

1 ( 1 )

3 ( 3 )

8 ( 6 )

Paranthesis indicate that figure of patients who feel the symptom

2. Chronic effects

Most of chronic effects of Cu attacked liver organ. Wilson disease is one of illustration of chronic consequence to do liver as the mark of toxicity. Accretion of Cu in the liver, indicated unable of enzyme that responsible to copper conveyance to egest it. Finally, there are extra of Cu which spill to blood, encephalon, kidney and cornea. Cirrhossis hepatic and neurological harm are illustration of apparent symptoms. Furthermore, wilson disease belong to have familial upset which is called ATP7B cistron. Hence, one who carriers this cistron will deduce the mutant on their kids without holding the symptoms.

Occupational exposure gives long term exposure due to people frequently work at metal industry. Copper dust may do several symptoms such as concern, chili, febrility, waterlessness on oral cavity and pharynx and metal smoke febrility. Workers who exposure to pesticide fumes non merely undergo those symptoms but besides lung ‘s disease viz. vineyard sprayers lung. Harmonizing to Menezes at al. , ( 2004 ) workers in startling industry were exposed by Cu smoke, dust and mist. Copper were found in their toenail, hair and piss.

Ingestion tract of Cu salts trough imbibing H2O delivers gastrointernal disease with nausea symptom. Systemic effects such as harm of haemolysis, liver and kidney are followed due to exposed to Cu salts ( Ellingsen et al, 2007 ) . By consuming 0.6-3.8 mg/l of Cu in imbibing H2O, hurting of abdominal followed by purging and diarrhoeas are occurred ( WHO, 1998 ) . At high concentration of Cu caused decease particularly to immature kids who exposed because of drawn-out imbibing H2O ingestion.

2.4.2 Effect on Biota

By and large, Cu sulfate is recognized as pesticide and weedkiller which can pollute H2O organic structures and finally up take by aquatic being. Chen & A ; Lin ( 2001 ) mentioned that Cu sulfate affects endurance, growing and eating of juvenile Panaeus Monodon in concentration 0.45 mg/l and 1 mg/l, severally.

Rauf and Javed ( 2007 ) revealed that H2O collected from River Ravi, Pakistan and plankton contains was contaminated by Cu. Furthermore, copper concentration in the H2O and plankton gives high important correlativity. Phaeodactylum tricornutum defines as Marine diatom which can be affected Cu toxicity in high concentration. Cid at al. , ( 1994 ) found 0.1 mg/l of Cu was inhibited growing of this alga which is 50 % decrease. Higher concentrations of Cu that reach 1 mg/l non merely disturb growing but besides affected photosynthesis and ATP production.

Copper besides brings perturbation embryo and egg of carp. The toxicity of Cu delivers unnatural development of embryo, distortion and finally decease of embryo of carp. This status decidedly reduces endurance of carp larvae. The experiment was conducted under dechlorinated tap H2O with temperature 22,2A°C and pH 7.8 ( A?ugowska and Witeska ) . By and large, Responses of aquatic beings to entire dissolved Cu in certain scopes are explained in Table 2.6

Table 2.6 Responses expected for assorted concentration scopes of coppera ( WHO, 1998 )

Entire dissolved Cu concentration scope ( Aµg/litre )

Effectss of high bioavailability in H2O

1-10

10-100

100-1000

& gt ; 1000

Significant effects are expected for diatoms and sensitive invertebrates, notably cladocerans. Effectss on fish could be important in fresh waters with low pH and hardness

Significant effects are expected on assorted species of microalgae, some species of macroalgae, and a scope of invertebrates, including crustaceans, univalves and sea urchins.

Survival of sensitive fish will be affected and a assortment of fish should demo sub deadly effects most systematic groups of macro algae and invertebrates will be badly affected. Deadly degrees for most fish species will be reached

deadly concentrations for the most tolerant beings are reached

a Sites chosen have moderate to high bioavailability similar to H2O used in most toxicity trials.

2.4.3 Plant

It has been identified that Cu give map as hint component for works to growing. Approximately 8 to 20 ppm Cu is needed bt workss. However, presence of Cu in high concentration still become job since this status causes inauspicious effects to works. There are dull of leaf colour bit by bit, chlorisis or mortification, roof growing perturbation and cut down outputs of workss. There was decrease growing of Rhodes grass ( Chloris gayana Knuth ) . The roots of this works was harm due to expose to copper concentration between 0.2 – 1 AµM ( Sheldon and Menzies, 2005 ) .

2.4.4 Microorganism

Copper in high concentration besides affected micro-organism particularly on their figure and population and diverseness. For case, concentration of Cu in surface H2O which is 0.01 mg/ml will cut down H2O column bacterium. In add-on, bacteriums which live in dirt will diminish ATP biomass production due to expose to 1000 pg/g Cu. Decrease of metabolic activities in line with cut downing figure of population because their biochemical activity was disturbed by altered environment status since Cu presence at high concentration ( Flemming and Trevors, 1989 ) .

2.5. Analytic method for Cu ( II ) ion

2.5.1 Atomic spectrometric

Copper measurings have been developed quickly. There are Flame Atomic Absorption Spectrophotometry ( FAAS ) , Electrothermal atomic soaking up spectrophotometry ( ETAAS ) , Inductively coupled Plasma Optical emanation spectrophotometry ( ICP-OES ) , and inductively conjugate mass spectrophotometry ( ICP-MS ) for Cu finding in biological samples and H2O samples ( Ellingsen et al. , 2007 ) . Analytic methods for Cu sensing in the fresh H2O samples are listed in Table 2.9.

Table 2.9. Common analytical methods of sensing Cu in the fresh H2O samples ( WHO, 1998 )

Sample Preparation

Method

Detection Limit

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