Treatment of Heavy Metals in Water Accompanied with Oil and A Soil Using some Expired Drugs at Al-Wahat/ Libya

for


3. Expired drugs
Used drugs and their numbers are illustrated in

Application for water accompanied with oil and soil
For the water accompanied with oil as wastewater: 10 mL of the drug was added to 50 mL of the water sample, and after precipitation, filtration and drying, the weight of all metal complexes was determined. For the soil sample: 100 g of soil sample dissolved in 1L distilled water overnight filtrated, then 10 mL of the drug was added to 50 mL of filtrates and left overnight, after precipitation, filtration and drying, the weight of all metal complexes was determined.

Results and Discussion
Many complexes of expired drugs have been formed by heavy metals, and this generally leads to a change in the properties of the original compound. The structure of expired drugs allows them to form metal complexes, and expired drugs often bind with divalent ions in a ratio of 1:1 or 1:2 (metal: ligand) and with trivalent ions, in a ratio of 1:1 or 1:3, rarely 1:2. Regardless of the metal ion and ligand concentration, complex molar ratio preferences may depend on the pH. Figure 1 explain that Laxofin forms a big precipitate with Cr ions more than other expired drugs, that the Laxofin drug contains Mg (OH)2 and possibly precipitated as Cr (OH)2. Moreover, Laxofin forms a big precipitate with Fe ions than other expired drugs due to precipitation as Fe (OH)3 [1]. Scopinal, Maxilase, and Becovit are able to form a big precipitate with Ni ions than other expired drugs due to its containing hyoscine butyl bromide and, vitamin B, which precipitated as Ni complexes. it is observed that, when the pH of an acidic solution of pyridoxol hydrochloride and nickel (II) was increased to pH 3.0, a greenish-blue color appeared, then the color intensity was increased as the pH rose to 6.0, in which a gelatinous precipitate was formed [2-7]. Becovit, Clara, multivitamins and Laxofin are able to form a big precipitate with Co than other expired drugs due to their containing vitamin B. The reaction of zinc acetate with thiamine hydrochloride (Vitamin B1) in water produced a Zn complex of Zn(thiamine)Cl3·0.4H2O. The resulting structure has been determined by X-ray diffraction. It was crystallizing with eight molecules in space group C2/c of the monoclinic system. The cell has dimensions at 20 °C of a = 25.747(8), b = 8.453(3), c = 17.402(4) Å, β = 105.8(1) °, V = 3644.3 Å 3 , Dcalc = 1.602 g cm −3 . The structure has been refined by least-squares methods to a final value of 0.037 [17]. Clara, Maxilase, Motilium and Scopinal are able to form a big precipitate with Zn than other expired drugs due to its containing Loratadine, α-amylase, Domperidone and, scopolamine butylbromide, which precipitated as Zn complexes [8][9][10][11][12][13][14][15]. Clara, Endocare Maxilase, Motilium Scopinal and Multivitamin are forming a big precipitate with Ag than other expired drugs due to its containing Loratadine, α-amylase, Domperidone scopolamine butyl bromide and, vitamins B which precipitated as Ag complexes [6-20].   [12][13][14][15][16][17][18][19][20].
Ampicillin can exist as a zwitterionic species. Protonated ampicillin AmpH2 + contains -COOH and the -NH3 + groups which are successively deprotonated in the pH range 2-4 and 6-8, respectively. Above pH 12, amp-tends to give a drawn-out buffer region, obviously due to partial deprotonation of the amide (-CONH-) moiety. At physiological pH, ampicillin remains in a fully deprotonated amp-form, which coordinates metal ions as an (N, O) bidentate ligand in the pH range 5 < pH < 8 using the amino nitrogen and the amide carbonyl oxygen atoms. The thiazolidine S atom is unlikely to coordinate this mode, obviously due to angle strain. The amide nitrogen can bind metal ions only on deprotonation. The (N, O) coordinated amp-undergoes amide deprotonation at pH > 8, and the resulting H~ amp2-ion coordinates as an (N, N, S) tridentate ligand using the amino nitrogen, deprotonated amide nitrogen, and the thiazolidine S atoms [4]. Table 2 explains the following trends:  The highest reacted heavy metal ions were Fe, Co, Cu, and Pb ions, which form the highest precipitates with Becovit expired drug.  The highest reacted heavy metal ions with Clara expired drug were Zn and Hg.  The highest reacted heavy metal ions with Drill expired drug were Cr, Co, Zn, Ag, Cd, and Pb ions, which form the highest precipitates.  The highest reacted heavy metal ions with Endocare expired drug were Cr, Ni, Zn, Ag, and Hg ions.  The highest reacted heavy metal ions with Gaviscon expired drug were Cr and Pb ions.
 Hedral expired drug form the highest heavy metal complex precipitates with Cr, Ni, Cu, Zn, and Cd ions [15].  The highest heavy metal ions that reacted with Laxofin expired drug were Cr, Cu, Cd, and Pb.  Maxilase expired drug form the highest heavy metal ions precipitate with Cr, Ni, Cu, Ag, Cd and Hg ions.  The highest reacted heavy metal ions with Motilium expired drug were Cr, Zn, Cd, and Pb ions.  The highest reacted heavy metal ions with Orapen expired drug were Cr, Cu, and Hg  Scopinal expired drug form the highest heavy metal complexes with Ni, Zn, Cd, Hg, and, Pb ions.  the highest-reacted heavy metal ions with Multivitamin expired drug were Fe, Co, Cu, Ag, Hg and Pb.  The Xilone expired drug formed the highest heavy metal complexes precipitate with Cr, Ni, Cu, Cd, and Hg ions. Some of the formation constants of the binary complexes of Ni (II), Co (II), Zn(I1) and Cd(I1) metal ions with Glygly were previously studied and suggested to form a stable hex-a coordinated species. Similarly, Zn (II) and Cd(II) form regular 1:1 and 2:1 species where Glygly was bidentate. These complexes were less stable than the corresponding glycine metal complexes. However, the inability of Zn (II) and Cd(I1) to deprotonate the peptidic proton may be due to the precipitation at a pH of 8.5 [18]. Table 3 explains that Becovit, Clara, Drill, Endocare, Gaviscon, Hedral, Laxofin, Maxilase, Motilium, Orapen, Scopinal, Multivitamin and Xilone are given large precipitations than other expired drugs due to their containing Sodium Alginate but others containing Vitamins B, Loratadine, Acetaminophen, sodium Alginate, Saponins, Magnesium Hydroxide, α-amylase, Domperidone, Penicillin V, Scopolamine butylbromide, Vitamins B and, Prednisolone. Figure 2 shows the comparison between the lowest molecular weight of the heavy metal used (Cr) and the highest molecular weight of the heavy metal used (Pb) with the same heavy metals found in oily water and soil that precipitate due to expired drugs. It was found that the water associated with oil contains a proportion of Very high heavy metals that is higher than standard solution Cr ion 520 ppm, Pb ion 2070 ppm, but soil with low heavy metal content is lower than standard solution Cr ion 520 ppm, and lead ion 2070 ppm.   Application for wastwater and soil with Pb wast water Soil Pb/2070ppm