P ARIPEX -INDIANJOURNALOFRESEARCH farming. entire nearly out chemical Tamilnadu eastern of In chemicals. , b controlled country arebeingwasted. tonnage (10.8MT)ofbitternfromdifferentsaltindustriesour strategic constituents s chloride of separation rejected more recovery With production a Chinese resource. cubic that alternate and 0.07% 1.1%, 7.5%, chloride elements chlorine over reported seawater 3.5% nutrients broadly inorganic terrestrially suspended s about The Introduction y Niva Nayak o f i t s t India, 36 d India: t e t which e e i r of industries Oceans u covers due m r ABSTRACT 99% the n emphasis m of miles w seawater 71 carbonate 1.8

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3 Seawater 98% ofdissolvedsolids.Thesixmajorionsconstitutingsolidinseawateraresodiumion(Na elements presentinbrineandbitterntorecovervariouseconomicallyimportantmarinechemicals.Brineconstitutemorethan sulphate in Bittern As classified

coast h . the c of the who c various of constitute at and development 54.8% from metals o If s industries i As a sources and processes. to and which holds are valuable The c % u conditions n of the n of 29-30 tons particles h minerals 4 and this l the derived bromide, 72% . s salt 5 Arabian

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), chloride(Cl like to viz. any is bittern (at with p Reed were the are and of then of of r between The characterise with of o Bridge bittern Mg, expect EDTA, The by in further the The chemicals. March. bittern It c like of 8M substantial to and to of innovative Boron. brine e where brine present of and this bottom and pH collected using was Indicator s are valuable artificial s distilled Sulfate, remove Ca, bittern. black-T NH AnalaR end known diluted KOH bittern e trace of .com In liquid s using KOH, study were were large rich high

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PARIPEX - INDIAN JOURNAL OF RESEARCH Volume-7 | Issue-7 | July-2018 | PRINT ISSN No 2250-1991 was used. In both the cases colour changes from wine red to blue. the ionic concentration9 and ionic mobility of the mineral content The Mg concentration was determined by subtracting the volume in solution. These conductive ions come from dissolved and obtained for Ca from the total Ca + Mg volume. inorganic materials such as , sulphides and carbonate compounds10. However, the electric conductivity of 290 Be' Bittern 2- 0 Estimation of Sulfate (SO4 ) (Gravimetric) is found to be 505000 µS/cm showing a lesser value than 26.5 Be' The diluted samples were precipitated near its boiling point as bittern. This may be due to the removal of NaCl during artificial 0 barium sulfate (BaSO4) in an acidic medium (HCl) by the addition of desalination from 26.5 to 29 Be'. barium chloride solution. The resulted precipitate was then boiled, filtered, washed with hot water until free of chloride. Then the Table 1. Comparision of pH and EC of brine and bittern precipitate was dried, ignited and weighed as BaSO . 0 0 0 4 Parameter Brine 2 Be' Bittern 26.5 Be' Bittern 29 Be' Estimation of Chloride pH 8.15 6.949 6.71 Chloride was estimated by Volhard's titration method. The sample EC μS/cm 26200 515000 505000 solution was treated with an excess of standard silver nitrate and The most abundant dissolved ions in seawater are sodium, the residual silver nitrate was determined by titration with chloride, magnesium, sulphate and calcium11. The concentrations standard thiocyanate using ferric alum (40% Ferric Ammonium of these ions are high due to the arrival of more salts by rivers with Sulfate with water) indicator. As the AgCl is more soluble than time. The analysis data for various important elements in brine and AgSCN, nitrobenzene is added for the coagulation of AgCl. The bittern are given in Table 2 & 3. It shows that with progressive sample solution was titrated until a permanent faint reddish- evaporation of sea brine the concentration of some major brown colouration appears. elements increases while some decreases. The concentration of 2- major elements like Mg, K and SO4 anion increases appreciably Atomic Absorption Spectrometry (AAS) with the increase in density. This is because Mg and K salt does not The elements namely Fe, Mn, Ni, Cr, Co and Sb are analysed by precipitate out below 290 Be'. The concentration of Ca falls with Atomic Absorption Spectrometer (Shimadzu model AA6300) rise in density and remains almost constant from 26.50 Be' to 290 where suitable hollow cathode lamps are used for the absorption Be' Bittern. In this study of artificial desalination the 290 Be' bittern of characteristic lines by the analyte and the concentration vs. shows the negligible concentration of calcium. This is due to the absorbance plot obeying the Beers - Lamberts law counts the fact that solid fractions of calcium carbonate and calcium sulphate concentrations of the corresponding elements. separated between 10-170 Be' and 17-240 Be' density, respectively and common salt within the density range of 24-290 Be' during Inductively Coupled Plasma Spectrometry (ICP-OES) solar evaporation or artificial desalination. This is due to very long The quantitative evaluation of elements like Al, Ti, Si, and B was residence times of sodium and chlorine in sea water, while calcium done by ICP (PERKIN ELMER, PLASMA-400) spectrophotometer. A (vital for carbonate formation) tends to precipitate much more high temperature (10,000K) Argon Plasma source is used for the quickly 12. This is further supported by Anthoni J.F. that can excitation of the element and the concentrations are measured as be made by evaporating sea water, may be artificially or naturally13. a function of the emission intensity of the emission spectra Major amount of sodium chloride is removed within density of 290 generated by the particular element. Be' and some percentage of sodium chloride is carried away with the waste liquor bittern showing higher concentration than 26.50 Estimation of Na & K Be'. This may be due to the presence of MgCl2, KCl and other The concentration of Na & K was determined by Flame Photometer 2- chloride bearing cations present in the bittern. Similarly, SO4 (ELICO - MODEL CL 22D) using specific filter for the wavelength of anion although is removed as calcium sulphate in the process of particular element. Calibration curves were made with suitable 2- evaporation, the SO4 content is also enriched. This may be standard solutions made from AR KCl and NaCl and the attributed due to the presence of magnesium and potassium as concentrations of the unknown samples were calculated. magnesium and potassium sulphate in the system. Several reports have been appeared on this aspect of utilisation and extraction of Results and Discussion valued chemicals from sea water 14. Solar evaporation is the cheapest and most economic means for the pre-concentration of sea-bittern. Hence in salt industries sea Table 2 : Major elements (gms/lit) in brine and bittern water is subjected to solar evaporation for recovery of salts. The 0 0 0 sea water and the bittern of 26.50 Be' collected after salt removal Major Elements Brine 2 Be' 26.5 Be' Bittern 29 Be' Bittern were subjected directly for analysis of pH, EC major and trace Mg 1.223 30.633 49.607 element. 1500 ml of 26.50 Be' bittern is further subjected to Ca 0.28 0.130 0.100 0 2- artificial desalination resulting 910 ml bittern of 29 Be' causing an SO4 1.983 42.82 64.70 appreciable volume reduction to 60.66 %. This desalinated bittern Cl- 18.73 185.389 191.979 was also analysed for pH, EC, major and trace elements. Na 4.5 73.75 53.75 K 0.1 7.313 10.875 The pH is one of the most important factors, which controls the aquatic environment. All the chemical and biological reactions are The presence of trace elements in seawater is generally due to the directly dependent upon the pH of the system. It is typically limited riverine inputs of weathering product of the exposed continent to a range between 7.5 and 8.4 6. The pH of collected sea water is and inputs resulting from the interaction of seawater with oceanic 8.15 whereas the 26.50 Be’bittern is ~ 6. 949. Similarly, for 290 Be' crust. It is observed from the table 3 that the concentration of Co, 0 bittern pH is found to be ~ 6.71 as shown in Table 1. Seawater is Cr, Fe, Mn and Sb increases from sea water to 26.5 Be' but the generally alkaline in nature. This alkalinity is due to the presence of concentration is found to be less in 290 Be'. Generally, - 2- - 7 3+ - the bicarbonates (HCO3 ), carbonates (CO3 ) and the (H2BO3 ) . occurs as Al (aq) under acidic conditions, and as Al(OH)4 (aq) During solar evaporation as the bicarbonates and carbonates are under neutral to conditions. Table 3 shows a less

removed as CaCO3, the pH of the bittern does not remain alkaline. concentration of Aluminium in seawater whereas the After removal of salt the 26.50 Be' bittern changes to 290 Be' where concentration of Al is not detected in 26.50 Be' and 290 Be' bittern. a slight decrease in pH is observed. Similarly, Silicon which remains as silicic acid in water is found to be 2.9mgs/l in the seawater and remains undetected in bittern.This Similarly, the sea water has a very high conductivity due to the may be due to co-precipitation with Na and Ca salts. The Boron amount of total dissolved salts. During artificial desalination or content in sea brine, bittern and marine by-product was also 14 volume reduction the water level decreases with increase of studied by Dhandhulika & Seshadri .Boron occurs as B(OH)3 (aq) or 8 - dissolved solids, thus contributing to higher conductivity values . B(OH)4 (aq) in seawater. Its concentration varies with a large The electrical conductivity of sea water is measured to be 26200 proportion as compared to the other trace elements. Also the µS/cm whereas it is 515000 μS/cm 26.50 Be' bittern due to the boron concentration is found to be higher than the other volume reduction during solar evaporation. It is dependent upon mentioned elements in bittern.

www.worldwidejournals.com 37 PARIPEX - INDIAN JOURNAL OF RESEARCH Volume-7 | Issue-7 | July-2018 | PRINT ISSN No 2250-1991 Table 3 : Trace elements (mgs/lit) in brine and bittern Trace Elements Brine 20 Be' 26.50 Be' Bittern 290 Be' Bittern Al 0.01 nd nd B 4.3 37.30 48.49 Co 0.11 4.67 2.65 Cr 0.20 2.01 1.74 Fe 0.20 7.9 7.0 Mn 0.21 0.99 0.68 Ni 0.16 0.03 0.1 Sb 0.0004 7.0 6.0 Si 2.9 nd nd Conclusion Indian Salt industry produced around 15.0 million tonnes of salt every year. Bittern generated in Salt industry contains enriched Potassium and magnesium salts in addition to other important chemicals. Potential recovery of chemicals from bittern in India has not been fully exploited. Considering significance of developing indigenous source of supply for and Magnesia which are important both for the Agricultural and strategic reasons, sea bittern could be utilized to recover potassium and magnesium. There are no viable land based Potash reserves in India but it has seawater, which is a possible source of Potassium salts although in low concentration. With no significant land based source of potash, India imports it’s entire requirement of potash. Besides potassium and magnesium, it is also possible to recover sodium chloride, sodium carbonate, bromine, and other strategic metals and chemicals out of this. But the processing routes have the further disadvantage that large quantities of seawater must be handled. So it is better to extract these salts from the bittern for which analysis of bittern plays the major role. In other way this can also simultaneously solve the disposal of such a huge quantity of waste generated at salt field.

References 1. Sverdrup H U, Jhonson M W and Fleming R H, The oceans, Their Physics, Chemistry and General Biology. (Prentice-Hall, Englewood Cliffs, N. J.) 1942, 1087. 2. Harvey H W, The Chemistry and Fertility of Sea Waters, (Cambridge Univ. Press London), 1960, 240. 3. Mero J L, The Mineral Resources of the Sea, In: Elsevier Oceanography Series , (Elsevier Publishing Company,Amsterdam-London- New York), 1965, 25. 4. Armstrong E F and Miall L M, Raw Materials from the Sea. (Chemical Publishing Co.,Brooklyn, N.Y.), 1946, 196. 5. Estefan, S. F.; Hydrometallurgy, 10(1)(1983) 39. 6. Chester J, Roy T, Marine Geochemistry. (Blackwell Publishing. ISBN 978-1-118- 34907-6) 2012. 7. James D B, Chemistry and Industry, 1977, 550. 8. LCRA, Indicators. In Colorado River Watch Network, 2014. 9. EPA 5.9 Conductivity. In Water: Monitoring and Assessment. 2012. 10. Miller R L, Bradford W L and Peters N E, Specific Conductance: Theoretical Considerations and Application to Analytical Quality Control. In U.S. Geological Survey Water-Supply,1988. 11. Hogan C M, Calcium. ed. A. Jorgensen A & Cleveland C, Encyclopedia of Earth National Council for Science and the Environment, 2010. 12. Pinet P R, Invitation to Oceanography.( St. Paul: West Publishing Company) 1996, 126. 13. Anthoni J F, Report of the Royal Society, 2005. 14. Dhandhukia M M and Seshadri K, Salt Res. & Ind., 7(4)(1970) 87.

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