BASIC CHEMICAL CADMIUM

LECTURER: Iryanti Fatyasari Nata, ST, MT, PhD

By Group 8 Name ID 1. Hj. Markiyah 2. Rima Sari Arisnawati 3. Sahla 4. Rony Santoso 5. M. Bagus Darmawan NIM H1E112024 NIM H1E112034 NIM H1E112206 NIM H1E112207 NIM H1E112212

MINISTRY OF NATIONAL EDUCATION UNIVERSITY OF LAMBUNG MANGKURAT ENGINEERING FACULTY ENVIRONMENTAL ENGINEERING DEPARTMENT BANJARBARU

2012

CHAPTER 1 INTRODUCTION

1.1. Description of Cadmium Cadmium is a chemical element with the symbol Cd and atomic number 48. This soft, bluish-white metal is chemically similar to the two other stable metals in group 12, zinc and mercury. Like zinc, it prefers oxidation state +2 in most of its compounds and like mercury it shows a low melting point compared to transition metals. Cadmium and its congeners are not always considered transition metals, in that they do not have partly filled d or f electron shells in the elemental or common oxidation states. The average concentration of cadmium in the Earth's crust is between 0.1 and 0.5 parts per million (ppm). Cadmium occurs as a minor component in most zinc ores and therefore is a byproduct of zinc production. It was used for a long time as a pigment and for corrosion resistant plating on steel while cadmium compounds were used to stabilize plastic. With the exception of its use in nickelcadmium batteries and cadmium telluride solar panels, the use of cadmium is generally decreasing. These declines have been due to competing technologies, cadmiums toxicity in certain forms and concentration and resulting regulations. Although cadmium has no known biological function in higher organisms, a cadmiumdependent carbonic anhydrase has been found in marine diatoms. Physical properties Cadmium is a soft, malleable, ductile, bluish-white divalent metal. It is similar in many respects to zinc but forms complex compounds. Unlike other metals, cadmium is resistant to corrosion and as a result it is used as a protective layer when deposited on other metals. As a bulk metal, cadmium is insoluble in water and is not flammable; however, in its powdered form it may burn and release toxic fumes.

Chemical properties Although cadmium usually has an oxidation state of +2, it also exists in the +1 state. Cadmium and its congeners are not always considered transition metals, in that they do not have partly filled d or f electron shells in the elemental or common oxidation states. Cadmium burns in air to form brown amorphous cadmium oxide (CdO); the crystalline form of this compound is a dark red which changes color when heated, similar to zinc oxide. Hydrochloric acid, sulfuric acid and nitric acid dissolve cadmium by forming cadmium chloride (CdCl2), cadmium sulfate (CdSO4), or cadmium nitrate (Cd(NO3)2). The oxidation state +1 can be reached by dissolving cadmium in a mixture of cadmium chloride and aluminium chloride, forming the Cd22+ cation, which is similar to the Hg22+ cation in mercury(I) chloride. Cd + CdCl2 + 2 AlCl3 Cd2(AlCl4)2 Isotopes Naturally occurring cadmium is composed of 8 isotopes. Two of them are naturally radioactive, and three are expected to decay but have not been experimentally confirmed to do so. The two natural radioactive isotopes are (beta decay, half-life is 7.7 1015 years) and
114 116 113

Cd

Cd (two-neutrino double beta

106

decay, half-life is 2.9 1019 years). The other three are electron capture), and life times have been set. At least three isotopes stable.
110

Cd, 108Cd (both double

111 112

Cd (double beta decay); only lower limits on their halfCd, Cd, and Cd are

Among the isotopes that do not occur naturally, the most long-lived are 109Cd with a half-life of 462.6 days, and
115

Cd with a half-life of 53.46 hours.

All of the remaining radioactive isotopes have half-lives that are less than 2.5 hours, and the majority of these have half-lives that are less than 5 minutes. Cadmium has 8 known meta states, with the most stable being years),
115m 113m

Cd (t = 14.1

Cd (t = 44.6 days), and

117m

Cd (t = 3.36 hours).

The known isotopes of cadmium range in atomic mass from 94.950 u ( Cd) to 131.946 u (132Cd). For isotopes lighter than 112 u, the primary decay mode is electron capture and the dominant decay product is element 47 (silver). Heavier isotopes decay mostly through beta emission producing element 49 (indium). One isotope of cadmium,
113 95

Cd, absorbs neutrons with very high

probability if they have an energy below the cadmium cut-off and transmits them otherwise. The cadmium cut-off is about 0.5 eV. Neutrons with energy below the cut-off are deemed slow neutrons, distinguishing them from intermediate and fast neutrons. Cadmium is created via the long s-process in low-medium mass stars with masses of 0.6 to 10 solar masses, which lasts thousands of years. It requires a silver atom to capture a neutron and then undergo beta decay History Cadmium was discovered simultaneously in 1817 by Friedrich Stromeyer and Karl Samuel Leberecht Hermann, both in Germany, as an impurity in zinc carbonate. Stromeyer found the new element as an impurity in zinc carbonate (calamine), and, for 100 years, Germany remained the only important producer of the metal. The metal was named after the Latin word for calamine, since the metal was found in this zinc compound. Stromeyer noted that some impure samples of calamine changed color when heated but pure calamine did not. He was persistent in studying these results and eventually isolated cadmium metal by roasting and reduction of the sulfide. The possibility to use cadmium yellow as pigment was recognized in the 1840s but the lack of cadmium limited this application. Aplication Even though cadmium and its compounds may be toxic in certain forms and concentrations, the British Pharmaceutical Codex from 1907 states that cadmium iodide was used as a medication to treat enlarged joints, scrofulous glands, and chilblains also laboratory uses. Cadmium has many common

industrial uses as it is a key component in battery production, is present in cadmium pigments, coatings, and is commonly used in electroplating. Cadmium also used as a barrier to control neutrons in nuclear fission. Cadmium oxide is used in black and white television phosphors and in the blue and green phosphors for color television picture t bes. Cadmium sulfide (CdS) is used as a photoconductive surface coating for photocopier drums.

CHAPTER 2 CONTENTS

2.1. Impacts of the Use of Cadmium Cadmium is an extremely toxic metal commonly found in industrial workplaces. Due to its low permissible exposure limit, overexposures may occur even in situations where trace quantities of cadmium are found. Cadmium is used extensively in electroplating, although the nature of the operation does not generally lead to overexposures. Cadmium is also found in some industrial paints and may represent a hazard when sprayed. Operations involving removal of cadmium paints by scraping or blasting may pose a significant hazard. Cadmium is also present in the manufacturing of some types of batteries. Exposures to cadmium are addressed in specific standards for the general industry, shipyard employment, construction industry, and the agricultural industry. 2.1.1. Impacts of the Use of Cadmium in the Environment Cadmium can mainly be found in the earth's crust. It always occurs in combination with zinc. Cadmium also consists in the industries as an inevitable by-product of zinc, lead and copper extraction. After being applied it enters the environment mainly through the ground, because it is found in manures and pesticides. Naturally a very large amount of cadmium is released into the environment, about 25,000 tons a year. About half of this cadmium is released into rivers through weathering of rocks and some cadmium is released into air through forest fires and volcanoes. The rest of the cadmium is released through human activities, such as manufacturing. Cadmium waste streams from the industries mainly end up in soils. The causes of these waste streams are for instance zinc production, phosphate ore implication and bio industrial manure. Cadmium waste streams may also enter the air through (household) waste combustion and burning of fossil fuels. Because of

regulations only little cadmium now enters the water through disposal of wastewater from households or industries. Another important source of cadmium emission is the production of artificial phosphate fertilizers. Part of the cadmium ends up in the soil after the fertilizer is applied on farmland and the rest of the cadmium ends up in surface waters when waste from fertilizer productions is dumped by production companies. Cadmium can be transported over great distances when it is absorbed by sludge. This cadmium-rich sludge can pollute surface waters as well as soils. Cadmium strongly adsorbs to organic matter in soils. When cadmium is present in soils it can be extremely dangerous, as the uptake through food will increase. Soils that are acidified enhance the cadmium uptake by plants. This is a potential danger to the animals that are dependent upon the plants for survival. Cadmium can accumulate in their bodies, especially when they eat multiple plants. Cows may have large amounts of cadmium in their kidneys due to this. In fresh water, cadmium toxicity is influenced by the hardness of the water, the softer the water the greater the toxicity. It has high short and long-term toxicity to aquatic life. No data are available on the short-term effects, or long term effects of cadmium on plants, birds, or land animals, excepting test animals, which did develop lung and testicle cancers. The same scarring of the lungs as found in humans will be present in very high doses in other mammals. Cadmium is highly persistent in the environment and will concentrate or bioaccumulate in aquatic animals. Industrial emissions of cadmium and or cadmium compounds can produce elevated, but still low-level concentrations in the atmosphere around the source. Motor vehicles may also produce elevated levels of cadmium in areas of higher traffic. Tobacco smoke is the primary source of cadmium indoors. Because of their short life expectancy in the atmosphere cadmium and its compounds are usually confined to the local area within which it is emitted.

2.1.2. Impacts of the Use of Cadmium in Living Things Human uptake of cadmium takes place mainly through food. Foodstuffs that are rich in cadmium can greatly increase the cadmium concentration in human bodies. Examples are liver, mushrooms, shellfish, mussels, cocoa powder and dried seaweed. The victims of this poisoning were almost exclusively postmenopausal women with low iron and other mineral body stores. Similar general population cadmium exposures in other parts of the world have not resulted in the same health problems because the populations maintained sufficient iron and other mineral levels. Thus, while cadmium is a major factor in the itai-itai disease in Japan, most researchers have concluded that it was one of several factors. Cadmium is one of six substances banned by the European Union's Restriction on Hazardous Substances (RoHS) directive, which bans certain hazardous substances in electrical and electronic equipment but allows for certain exemptions and exclusions from the scope of the law. Although some studies linked exposure to cadmium with lung and prostate cancer, there is still a substantial controversy about the carcinogenicity of cadmium. More recent studies suggest that arsenic rather than cadmium may lead to the increased lung cancer mortality rates. Furthermore, most data regarding the carcinogenicity of cadmium rely on research confounded by the presence of other carcinogenic substances. Tobacco smoking is the most important single source of cadmium exposure in the general population. It has been estimated that about 10% of the cadmium content of a cigarette is inhaled through smoking. The absorption of cadmium from the lungs is much more effective than that from the gut, and as much as 50% of the cadmium inhaled via cigarette smoke may be absorbed. On average, smokers have 45 times higher blood cadmium concentrations and 23 times higher kidney cadmium concentrations than nonsmokers. Despite the high cadmium content in cigarette smoke, there seems to be little exposure to cadmium from passive smoking. No significant effect on blood

cadmium concentrations has been detected in children exposed to environmental tobacco smoke. Cadmium exposure is a risk factor associated with early atherosclerosis and hypertension, which can both lead to cardiovascular disease. In other cases, soils that are acidified enhance the cadmium uptake by plants. This is a potential danger to the animals that are dependent upon the plants for survival. Cadmium can accumulate in their bodies, especially when they eat multiple plants. Cows may have large amounts of cadmium in their kidneys due to this. Earthworms and other essential soil organisms are extremely susceptive to cadmium poisoning. They can die at very low concentrations and this has consequences for the soil structure. When cadmium concentrations in soils are high they can influence soil processes of microrganisms and threat the whole soil ecosystem. In aquatic ecosystems cadmium can bio accumulate in mussels, oysters, shrimps, lobsters and fish. The susceptibility to cadmium can vary greatly between aquatic organisms. Salt-water organisms are known to be more resistant to cadmium poisoning than freshwater organisms. Animals eating or drinking cadmium sometimes get high blood-pressures, liver disease and nerve or brain damage.

2.2. Efforts to Control Cadmium Pollution Efforts to tackle heavy metal pollution can actually be done using a chemical process. Such as the addition of certain chemical compounds for the separation of heavy metal ions or the ion exchange resin , and several other methods such as absorption using activated carbon, reverse osmosis and electrodialysis. However, this process is relatively expensive and tend to cause new problems, namely the accumulation of these compounds in sediment and aquatic organisms.

Handling of heavy metals by microorganisms or microbial (in terms of biology known as bioaccumulation, bioremediation, or bioremoval), an alternative that can be done to reduce the toxicity of heavy metal elements in the aquatic environment. Method or technology is very exciting to be developed and implemented, because it has advantages over chemical processes. Several studies have reported on the use of microorganisms to tackle heavy metal pollution more effectively than the ion exchange and reverse osmosis in relation to the sensitivity of the presence of dissolved solids (suspended solids), organic matter and other heavy metals. As well, better than the deposition process (presipitation) that is associated with the ability to stimulate changes in pH and heavy metal concentrations. In other words, the handling of heavy metals by microorganisms is relatively easy to do, inexpensive and tend to be harmful to the environment. Cellular organisms sianobakteria a cellular organism belonging microalgae or micro algae. In nature, the organism is widespread both in freshwater and sea. To date approximately 2,000 species known sianobakteria scattered in various habitats. Based on recent r esearch, sianobakteria is one of the organisms that are known to accumulate (absorb) certain heavy metals such as Hg, Cd and Pb. Suhendrayatna (2001) in his paper, describes in more detail about the process of absorption of heavy metal ions by sianobakteria and microorganisms in general. Generally, the absorption of heavy metal ions by microorganisms sianobakteria and consists of two mechanisms involving the active uptake (biosorption) and passive uptake (bioaccumulation). a. Active uptake process This process can also occur in various types of living cells. This mechanism occurs simultaneously along with the consumption of metal ions to sianobakteria growth, and / or accumulation of intracellular metal ion. Heavy metals can also be deposited on the metabolism and cell ekresi on the second level. This process depends on the energy contained and sensitivity to different parameters such as pH, temperature, ionic strength, light, and others.

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However, this process can also be inhibited by low temperatures, lack of energy sources and inhibitors of cell metabolism. This event, as shown by the accumulation of cadmium in the cell wall of Chlorella vulgaris Ankistrodesmus and reaching about 80 degrees of total accumulation in the cells, whereas the arsenic binds to the cell wall of Chlorella vulgaris average of 26 percent. Suhendrayatna (2001) adds, to design a processing waste containing heavy metal ions involving sianobakteria relatively easy to do. The first process, sianobakteria put option, grown and then brought into contact with water contaminated heavy metal ions. Pengontakkan process done in a certain time period is intended to allow sianobakteria interact with heavy metal ions, further sianobakteria biomass is separated from the liquid. The last process, biomass sianobakteria bound with heavy metal ions are regenerated for reuse or disposed of into the environment later. Utilization sianobakteria to tackle heavy metal pollution is a very interesting thing to do, either by the public, government and industry. Because cellular organisms sianobakteria is easy to find, has a very broad spectrum of habitats, can grow quickly and require no specific requirements for life, easily cultivated in aquaculture systems. b. Passive uptake process This process occurs when heavy metal ions bound to the cell wall biosorben. Passive uptake mechanism can be done in two ways, first by ion exchange in which ions in the cell walls were replaced by heavy metal ions, and the second is the formation of complexes between heavy metal ions with functional groups such as carbonyl, amino, thiol, hydroxy, phosphate, and hydroxy-carboxyl and forth and quickly. An example is the Sargassum sp. and Eklonia sp. where Cr (6) experienced a reduction reaction at low pH to Cr (3) and Cr (3) in-remove through cation exchange process.

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CHAPTER 3 CONCLUSION

Cadmium present in small amounts in the environment but extremely harmful effects on health. Cadmium can pollute soil, water, and air. Extensive cadmium pollution can cause plant, animal and human contamination. In animals and humans, cadmium can cause organ damage resulting in lower health and cause death. Cadmium contamination in the environment needs to watch out because it can reduce the quality of life of living beings. Efforts to tackle heavy metal pollution can actually be done using a chemical process. Such as the addition of certain chemical compounds for the separation of heavy metal ions or the ion exchange resin. Handling of heavy metals by microorganisms or microbial (in terms of biology known as bioaccumulation, bioremediation, or bioremoval), an alternative that can be done to reduce the toxicity of heavy metal elements in the aquatic environment. the absorption of heavy metal ions by microorganisms sianobakteria and consists of two mechanisms involving the active uptake (biosorption) and passive uptake (bioaccumulation).

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REFERENCES

Cadmium and compounds: Environmental effects http://www.npi.gov.au/substances/cadmium/environmental.html Accessed on November 18, 2012 Cadmium: Biological Effects and Occurrence in the Environment http://www.annualreviews.org/doi/abs/10.1146/annurev.pa.15.040175. 002233?journalCode=pharmtox.1 Accessed on November 18, 2012 Cadmium - Cd http://www.lenntech.com/periodic/elements/cd.htm Accessed on November 18, 2012 Logam Berat Sebagai Penyumbang Pencemaran Air Laut http://masdony.wordpress.com/2009/04/19/logam-berat-sebagaipenyumbang-pencemaran-air-laut/ Accessed on November 18, 2012

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