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Arsenic and Selenium- Contamination in Food Chains, Hazards, Determination

Aman Paul, Dorcus Masih, Sachin Verma, Sajan Palanchoke, Priyanka Malik, Dr Justin Masih M.Tech (Food Technology) Scholars, Department of Food Process Engineering, SHIATS (Allahabad) M.Sc (Dairy Technology) Scholar, Department of Dairy Technology, SHIATS (Allahabad) R & D Executive, Field Fresh Foods Limited (Gurgaon) Assistant Professor, Department of Food Process Engineering, SHIATS (Allahabad) Assistant Professor, Department of Chemistry, ECC (Allahabad)

Arsenic and Selenium- Availability and Contamination in Food Chains


Arsenic is a naturally occurring dissolved element in ground and surface water throughout the world. Arsenic and its compound often have garlic like odour, when crushed or when scratched with hard object. Arsenic compounds can be very toxic and their uses are strictly controlled by health and environmental regulations (1). Erosion of arsenic containing surface rocks probably account for a significant amount of arsenic in water supplies. The other major sources of environmental arsenic are the smelting of non-ferrous metal ores, especially copper. Arsenic is an essential nutrient and is a constituent of many foods such as meat, fish, poultry, grains and cereals (2). The concentration of arsenic in plants can vary depending on factors like the species of plant, the type of arsenic in soil, and the location of a given species. Arsenic can exist in a variety of oxidation states in inorganic and organic forms in many environmental matrices such as natural water and soils (3). Selenium is widely present in nature in relatively small concentrations in rocks, plants, coal and other fossil fuels (4). Selenium is also present in the soil in certain areas of the USA (the dry plains of Dakota, Wyoming and Kansas) and is taken up by vegetation which then becomes poisonous to animals; their meat is rendered unfit for human consumption. Selenium is however, an essential trace element in some animal diets (5). It has both toxicological and physiological effects (6,7). The toxicity, availability and environmental mobility of selenium are very much dependent on its chemical forms (8). Selenium can occur in different oxidation states in organic and inorganic forms. In many environment matrices, example natural water, soil, etc. the predominant oxidation states of selenium are Se (IV) and Se (VI) (9). Selenium is a trace mineral that is essential to good health but required only in small amounts (10,11). Selenium is incorporated into proteins to make selenoprotiens, which are important antioxidant enzymes. The antioxidant properties of selenoprotiens help to prevent cellular damages from free radicals. Free radicals are natural by-products of oxygen metabolism that may contribute to development of chronic diseases such as cancer and heart diseases (12,13). Other selenoprotiens help to regulate thyroid function and play a role in the immune system (14-16).

Hazards from Arsenic and Selenium


In excessive amounts, arsenic causes gastrointestinal damage and cardiac damage. Chronic doses can cause vascular disorders such as Blackfoot disease. Arsenic and its compounds are reported to be carcinogenic, mutagenic and teratogenic in nature (2). The most infamous use of arsenic is as a poison. However, arsenic can now be detected during autopsy, so this use of the element has become a legend of the past. These days the most important use of arsenic is in the preservation of wood. Arsenic is also used as a weed killer and rat poison (18). High concentration of selenium causes pulmonary edema, abdominal pain, jaundice, chronic gastrointestinal diseases, hair loss and fatigue in humans (19) and its deficiency causes Keshan and Kaschin Beck diseases in humans, which are frequently reported in China (20). It also plays a major role in the life cycle of plants (cruceferal family), which absorb organoselenium compounds accumulated in the soils of semiarid areas and may poison livestock that graze on them (21). Some industrial and agricultural processes release selenium as a by-product and selenium from such sources has caused environmental disaster (22). Therefore, understanding the acute toxicity of both metals which are in fewer considerations, it becomes really important for us to develop new and rapid techniques to determine the amounts of arsenic and selenium present in the foods we eat.

Materials and Methods


1. Arsenic Apparatus- A Systronics 2201 UV-Visible Double Beam Spectrophotometer with 1 cm quartz cell and a pH meter are required. Reagents and Solutions- All chemicals are of analytical reagent grade or chemically pure grade and distilled water is used throughout the study. Arsenic (III) stock solution (1000 gm/l) is prepared by dissolving 0.1734 g of NaAsO2 in 100 ml of water. Working standard is prepared by appropriate dilution of stock. Toluidine blue (0.01 %), hydrochloric acid (1 M), potassium iodate (2 %) HNO3, perchloric acid and sodium acetate (1 M) are used. Methodology-A sample of plant material (grass5g) is digested with 10 ml of HNO3 for about 25 minutes. After cooling, 1 ml of perchloric acid is added and heating is continued for about another 10 minutes. Arsenic (V) if any was reduced to As (III) by the process described. The solution was transferred to a 25 mL volumetric flask and diluted to volume with water. Aliquots of sample solution containing 1.2-10.5 gm/l of arsenic (III)] are transferred in to a series of 10 ml calibrated flasks. Potassium iodate (2 %, 1 ml), then hydrochloric acid (1 M, 1 ml) is added and mixture was gently shaken until the appearance of yellow colour indicating the liberation of iodine. This is followed by addition of toluidine blue (0.01 %, 0.5 ml) and 2 ml of sodium acetate solution. The solution is kept for 2 minutes and made up to the mark with distilled water. The absorbance is measured at 628 nm against the corresponding reagent blank. Reagent blank is prepared by replacing the analyte (arsenic) solution with distilled water. The absorbance corresponding to the bleached colour, which in turn corresponds to the analyte (arsenic) concentration, is obtained by subtracting the absorbance of the blank solution from that of the test solution. The amount of the arsenic present in the volume taken is computed from the calibration graph (23).

2. Selenium Apparatus- A Systronics 2201 UV-Visible Double Beam Spectrophotometer with 1 cm quartz cell and a pH meter are required. Reagents and Solutions- All chemicals are of analytical reagent grade or chemically pure grade and double distilled water is used throughout the study. A standard stock solution of selenium is prepared by dissolving 1.912 g of NaHSeO3 in 1000 ml of water and standardized by the dithiozone method (42). Toluidine blue solution (0.02%), potassium iodide (2%), hydrochloric acid (1M), EDTA acetate buffer solution (pH=4) are used. Methodology- A known weight (50.0 g) of a sludge sample was placed in a 50 ml beaker and extracted 4 times with a 5 ml portion of concentrated HCl. The extract was boiled for 10 minutes to convert any Se (VI) present in the soil to Se (IV) cooled and neutralized (pH 7) with 10% NaOH. A volume of 5 mL of 5 % EDTA solution was added and the contents were made up to 25 ml with water. Aliquots of sample solution containing 1.016.0 gm/l] of selenium solution are transferred into a series of 10 ml calibrated flasks. A volume of 1 ml of 2 % potassium iodide solution is added followed by 1 ml of 1 M hydrochloric acid and the mixture was gently shaken until the appearance of yellow colour, indicating the liberation of iodine. A 0.5 ml of 0.02 % toluidine blue solution is then added to it followed by the addition of 2 ml of acetate buffer solution of pH=4 and the reaction mixture shaken for 2 minutes. The contents are diluted to 10 ml with distilled water and mixed well. The absorbance of the resulting solutions is measured at 628 nm against the corresponding reagent blank. A reagent blank is prepared by replacing the analyte (selenium) solution with distilled water. The absorbance corresponding to the bleached colour which in turn corresponds to the analyte (selenium) concentration is obtained by subtracting the absorbance of the blank solution from that of test solution. The amount of the selenium present in the volume taken was computed from the calibration graph. (24)

Conclusion
Arsenic is a naturally occurring dissolved element in ground and surface water throughout the world. Selenium is widely present in nature in relatively small concentrations in rocks, plants, coal and other fossil fuels. Both arsenic and selenium can be very hazardous substances when consumed in overdoses. They can be detected in food by simple UV-Vis spectrophotometer based technique. UV-Vis spectrophotometer enables quick detection of the arsenic and selenium in food stuff.

References
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