To Study the Effect of of Chromium (III) and Iron (II) on Black Currant Leaves Department of Chemistry, Yobe State University, Damaturu, Nigeria ABSTRACT An environmental friendly method for adsorption of Cr(III) and Fe(II) has been investigated using black currant leaves. The effect of ph on adsorption of the studied analyte has been investigated. The results of the study indicated a maximum adsorption of 55% for Cr(III) at ph 5 and maximum adsorption of 56% for Fe(II) at ph 4. The target analytes were determined by Wagtech Photometer 7100. Keywords: Black currant, adsorption, analytes, target, temperate. INTRODUCTION There is an increasing interest in the inclusion of berries, especially the black currant in the human diet mainly for the health benefits associated with their consumption. Black currant (Ribes nigrum L.) belonging to the genus Ribes is widely cultivated across temperate Europe, Russia, New Zealand, parts of Asia and to a lesser extent North America. Besides high content of tasty juice, black currant is a valuable source of bioactive compounds like vitamin C and polyphenols, acting as antioxidants, with a potential to protect against disorders such as cardiovascular events, cancer and other degenerative symptoms. Industrially, black currant fruits are considered to be of importance; however other anatomical parts like buds and leaves are also excellent sources of phenolic compounds. The leaf and bud extracts are of relevance as raw material for the food and health industry thereby making black currant a lucrative product for use as functional food ingredient. Research until now has investigated the content of different polyphenolic fractions of the fruits and to lesser extent on content of these fractions on plant parts like buds and leaves. The breeding of black currant is mainly focussed on national and international requirements, as related to specific quality desired from the processing sector alongside with important agronomic characters. Black currant cultivation is in different areas limited by a lack of climate adaptation in the existing cultivars as well as susceptibility of these cultivars to different pests and diseases. Also, the levels of bioactive compounds in black currant like content of ascorbic acid and polyphenols are influenced by genotype, environment and genotype x environment interactions. Durable resistance towards damaging pest and diseases together with an increase in content of health promoting compounds and adaptability to local climates remain to be of high priority for breeders. Additionally flavour, mouth feel, aroma and after taste are important primary quality factors for the fresh fruit market and juice industry. The black currant can be eaten raw but are usually cooked in variety of sweet savoury dishes. They are used to make Jams Jellies and syrups and are grown commercially for the juice market. The fruit is also used in the preparation of alcoholic beverages and both fruits and foliage have uses in traditional medicine and the preparation of dyes. Black currant dried leaf is used for arthritis, gout, joint pain (rheumatism), diarrhoea, colic, hepatitis and liver ailments, convulsions and disorders that caused swelling (inflammation) of the mouth and throat. Black currant dried leaf is also used for treating coughs, cold and whooping, disinfecting the urine promoting urine flow, and treating bladder stones. While some people apply black currant leaf directly to the skin for treating wounds and insect bites. Black currant leaves are said to be an incredible immune booster. Black currant leaves are diaphoretic and diuretic. They aid in the elimination of reduction of bodily fluids and they are believed to lower vascular pressure. The leaf infusion is also believed to stimulate the nervous system and may help with stress related ailments. Black currant leaves contain glycosides, essential oil, essential fatty acids, enzymes, Vitamin C and other vital nutrients. They also stimulate better heart health maintenance and respiratory. Also black currant is a plant used the seed oil, leaves, fruits and the flowers to make medicine. Its leaves are also bactericidal which allows them to be used as an infusion (tea) externally to treat abscesses. These leaves are easy to grow and can be propagated easily from cutting. In some other country (e.g. Russia) 44
the black currant leaves may be used for flavoring tea or preserver such as salted cucumbers, making a deep greenish yellow beverage while in Europe the leaves have traditionally been used for arthritis, spasmodic cough, diarrhoea. Black currant also used in alternative medicine, due to its side effects, tea made from the dried leaves of blackcurrant is used to treat bladder disorders in folk medicine as well as rheumatoid pain and joint disease in addition to its diuretic effect of retaining potash salt. The chemical composition of the leaves seed has been determine using various analytical methods and the different methods give rise to differences in reported concentrations of each components. There appear a variation of chemical content within the species but not necessary as a consequence of cultivation method. Figure.1. Black Currant Plant. Chromium and Iron are continuously released into natural environment due to industrial activities, weathering of rocks and soils, combustion of fossil fuels, agricultural activities, atmospheric emission, and mining activities. Speciation analysis of trace amounts of chromium ions has become an important topic in environmental and biological science. It is well known that the toxicological and biological properties of most elements depend upon their chemical forms. Therefore, the knowledge on the speciation of chromium is of particular necessity. Chromium is widely used in various industries, such as plating, tanning, paint and pigment production, and metallurgy, which possibly contaminate the environment. Chromium (III) compounds are one of the essential trace nutrients in human bodies and play an important role in the metabolism of glucose and certain lipids, whereas chromium (VI) compound are toxic and carcinogenic. The United State Environmental Protection Agency (USEPA) has regulated the permissible limit of 0.1 mgl -1 of total Chromium in drinking water. In Japan, the maximum tolerable concentration of Chromium in waste water is 0.5 and 0.05 mgl -1 for total chromium. The element Chromium occurs in natural samples in two relatively stable valence states, i.e. in the form of Cr (III) and Cr(VI) species, which exert quit different effects on biological system. In fact, while Cr (III) is an essential component having an important role in the glucose, lipid and protein metabolism, Cr (VI) has a definitely adverse impact on living organism. Cr (VI) can easily penetrate the cell wall and exert itself. The importance of Chromium speciation in plants may be illustrated by the fact that, to maintain good health, humans require an adequate daily intake of nutrients, including essential trace elements such as chromium, cobalt, copper, iodine, iron, manganese, molybdenum, selenium, zinc and several other micro-elements found mostly in vegetables. It is therefore essential to ascertain in which form Chromium is present in plant tissues as well as the extent of their accumulation, because plant derived Chromium containing food materials, primarily from vegetable crops, provide a major portion of the daily Chromium intake. Another example of the importance of Cr (VI) speciation is connected with the possibility of its presence in medicinal plants [1-8]. Since one of the routes of Chromium incorporation into the human body is by ingestion, several analytical methods have been developed in order to separate and determine Cr (III) and Cr(VI) species in water samples. The concentration of Chromium in natural water is very low, in order of a few µgl -1, therefore powerful techniques are required but of those currently available only a few show sufficient detection power. 45
Despite the fact that iron is the second most abundant metal in the earth crust, iron deficiency is the world s common cause of anaemia. When it comes to life, iron is more precious than gold. The body hoards the element so effectively that over millions of years of evolution, humans have developed no physiological means of iron extraction. Iron adsorption is the sole mechanism by which iron stores are physiologically manipulated. The average adult stores about 1 to 3 grams of iron in his or her body. An exquisite balance between dietary uptake and loss maintains this balance. About 1 mg of iron is lost each day through sloughing of cell from skin and mucosal surfaces, including the lining of the gastrointestinal tract. The Botanical description of Black currant is given below: Common names: European blackcurrant, Blackcurrant Quincy berries, Siyar Frankuzumu. Scientific name : Ribes Nigrum Family :Grossulariaceae currant Synonyms : Saxifragaceae (Original family) MATERIALS AND METHOD Materials Mechines Wagtech photometer 7100 modal, Centrifuge mechine TDL 50B and 3505 JENWAY ph meter. Reagents Ferrous Chloride (FeCl 2 ), Chromium Chloride (CrCl 3 ), Hydrochloric acid (HCl) (M.W. = 36.46, density= 1.18 g), Sulphuric acid (H 2 SO 4 ) (purity %= 98%, M. W. = 98), Ammonia solution (NH 3 ) (M.W =17.03). Preparation of solution One gram of Ferrous Chloride was dissolved in 20% of Sulphuric acid and the solution was made to one litre in a one litre measuring flask. Also, 1.0 g of Chromium Chloride was dissolved in one litre measuring flask. One molar Hydrochloric acid was prepared in one litre. METHOD (i) The fresh leaves of black currant were collected from black currant plant. The leaves of black currant were dried in air and make powder by crushing or grinding with mortar and pestle and then stored for future use as absorbent. (ii) 2ml of ferrous chloride solution was measured and also adjust the ph from 1 to 6 by using 1molar solution of HCl and NH 3 solution. (iii) To 10 ml of each of the prepared solution into a clean test tube separately according to their ph range, add about 0.5g black currant leaves powder into each of the test tube. (iv) The test tubes were centrifuged at 500 rpm for 10 minutes and pipette out 5 ml of the supernatant into clean test tube. (v) One H.R. iron tablet was added into each supernatant obtained from step (iv) above and kept to stand for a minute to allow full colour formation. (vi) An appropriate wavelength of the analytes was selected on a Wagtech photometer and the sample was inserted into the photometer separately and the results were recorded respectively. (vii) Repeat the above procedure using chromium chloride instead of ferrous chloride and record the results from the photometer. (viii) During the process the above procedure was repeated for blank determination without the analytes of the data analysis, all values obtained were corrected by subtracting the values of procedural blank. RESULTS AND DISCUSSION RESULTS 46
Table 1: The ph and sample solution of Cr(III) in supernatant and in blank solution (without sample) at ph 1 to 6. Also the Cr(III) adsorbed by the sample and percentage. ph Mean ± SD in supernatant Mean ± SD in blank solution Average(blank solution- supernatant) (%) 1 0.69 ± 0.49 1.61 ± 1.08 1.61 0.69 = 0.92 46 100-46=54 2 0.73 ± 0.52 1.69 ± 1.19 1.69 0.73 = 0.96 48 100-48=52 3 0.82 ± 0.58 1.73 ± 0.49 1.73 0.82 = 0.91 46 100-46=54 4 0.92 ± 0.65 1.86 ± 1.72 1.86 0.92 = 0.94 47 100-47=53 5 0.95 ± 0.67 1.84 ± 1.30 1.84 0.95 = 0.89 45 100-45=55 6 0.84 ± 0.59 1.75 ± 1.23 1.75 0.84 = 0.91 46 100-46=54 Calculations The original sample used was 2ppm therefore to calculate % record after adsorption according to the ph given below: ph 1 = 0.92x100/2=46%, ph 2 = 0.96x100/2=48%, ph 3 =0.91x100/2=45.5%, ph 4 =0.94x100/2=47%, ph 5 =0.89x100/2=44.5%, ph 6 =0.91x100/2 =45.5%. Effect of ph on adsorption of Cr(III) Based on the experiment conducted, the result indicated that the maximum adsorption of 55% was obtained at ph=5. Table 2: The ph and sample solution of Fe(II) in supernatant and in blank solution (without sample) at ph 1 to 6. Also the Fe(II) Adsorbed and percentage. ph Mean ± SD in supernatant (µgl - 1 ) Mean ± SD in blank solution Average(Blank solution- Supernatant) (%) 1 0.53 ± 0.45 1.43 ± 1.01 1.43-0.53=0.90 45 100-45=55 2 0.64 ± 0.56 1.56 ± 1.10 1.56-0.64=0.92 46 100-46=54 3 0.75 ± 0.58 1.65 ± 1.16 1.65-0.75=0.90 45 100-45=55 4 0.83 ± 0.58 1.72 ± 1.21 1.72-0.84=0.88 44 100-44=56 5 0.83 ± 0.58 1.73 ± 1.22 1.73-0.83=0.90 45 100-45=55 6 0.73 ± 0.51 1.66± 1.17 1.66-0.73=0.93 47 100-47=53 Calculations The original sample used was 2ppm therefore to calculate % record after adsorption according to the ph range given below: ph 1 = 0.90x100/2=45, ph 2 =0.92x100/2=46, ph 3 =0.90x100/2 =45, ph 4 =0.88x100/2 =44, ph 5 =0.90x100/2=45, ph 6 =0.93x100/2=47. Effect of ph on adsorption of Fe(II) Effect of ph on adsorption of Fe(II) on black currant leaves has been studied[9-16]. The ph of the sample solution containing 2µgl -1 of the analyte was adjusted to a ph range of (1-6) by adding 1mol l -1 ammonia solution or HCl. As could be seen, the maximum adsorption 56% was obtained at ph=4. 47
CONCLUSIONS The effect of ph showed that the maximum 55% uptake capacity for Cr(III) was at ph 5 and while 56% for Fe(II) was observed at ph 4. Since black currant leaves are highly abundant and show a good adsorption capacity for Cr(III) and Fe(II) ions, black currant leaves can be alternative low cost adsorbent to remove Cr(III) and Fe(II) from environment. REFERENCES 1. Verma, P.C. 2015. An adsorption study of Cr(III) and Fe(II) on Khaya Senegalansis leaves (Mahogany). Intl. J. Basic and Applied Biology, 2(4), 193. 2. Singh, R., Gautam N., Mishra, A. and Gupta, R. 2011. Heavy metals and living systems: An overview, Indian J. Pharm., 43, 246-253. 3.5 Kadirvelu, K., Thamaraiselvi, K. and Namasivayam, C. 2001. Removal of Heavy Metal from Industrial Waste waters by onto Activated Carbon Prepared from an Agricultural Solid Waste. Bio- resource Tech., 76, 63-65. 4. Khan, N.S., Ibrahim, S. and Subramaniam, P. 2004. Elimination of heavy metals from wastewater using agricultural wastes as adsorbents, Malaysian J. Sci., 23, 43-51. 5. Salim, R., Al-Subu M., Abu Shqair, I. and Braik, H. 2003. Removal of zinc from aqueous solution by dry plant leaves, Instituti of Chemical Engineers Trans ICHEME, 81 Part B. 6. Venkateswarlu, P., Ratnam, M.V., Rao, D. S. and Rao, M. V. 2007. Removal of chromium from an aqueous solution from Azadirachta indica (neem) leaf powder as an adsorbent, Intl. J. Physic Sci., 2, 188-195. 7. Verma, T., Garg, S.K. and Ramteke, P.W. 2009.Genetic correlation between chromium resistance and reduction in Bacill brevis isolated from tannery effluent, J Appl. Microbiol.,107, 1425 1432. 8. Modrogan, C., Miron, A.R., Orbulet, O.D. and Costache, C.M. 2010. Removal of Nitrate and Hexavalent Chromium from Ground water Using Zerovalent Iron A Laboratory Study, Bulletin UASVM Agriculture, 67(2), 80-86. 9. Krishna, D., Siva Krishna, K. and Padma, S.R. 2013. Response Surface Modeling and Optimization of Chromium (III)Removal from Aqueous Solution Using Borasus Flabellifer Coir Powder, International J. Appl. Sci. and Engineering, 11(2), 213-226. 10. Ngah, W.S.W., Ghani, S.A. and Kamari, A. 2005. behavior of Fe(II) and Fe(III) ions in aqueous solution on chitosan and cross-linked chitosan beads, Bio-resource Tech., 96, 443-450. 11. Ahalya, N., Kanamadi, R.D. and Ramachandra, T.V. 2006. Biosorption of Chromium (VI) by Tamarindus indica pod shells, Journal of Environmental Science Research International, 1(2), 77-81. 12. Tofan, L., Paduraru, C., Volf, I. and Toma, O. 2011. Waste of Rapeseed from biodiesel production as a potential biosorbent for heavy metal ions, Bio-resources, 6(4), 3727-3741. 13. Kumar, A.V.A., Darwish, N.A. and Hilal, N. 2009. Study of various parameters in the biosorption of heavy metals on activated sludge, World Appl. Sci. J., 5, 32-40. 14. Kumar, P.S. and Gayathri, R. 2009. of Pb 2+ ions from aqueous solutions onto bael tree leaf powder: isotherms, kinetics and thermodynamics study, J. Eng. Sci. and Tech., 4, 381-399. 15. Rose, E.P. and Rajam, S. 2012. Equilibrium study of the adsorption of Iron(II) ions from aqueous solution on carbons from wild jack and jambul, Adv. in Appl. Sci. Research, 3(2), 1889-1894. 16. Thilagavathy, P. and Santhi, T. 2013. Sorption of Toxic Cr(VI) From Aqueous Solutions by Using Treated Acacia nilotica Leaf as Adsorbent: Single and Binary System, Bio-resources, 8(2), 1813-1830. 48