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The Application of the Potentiometric Stripping Analysis to Determine Traces of M(II) Metals (Cu, Zn, Pb and Cd) in Bioinorganic and Similar Materials 229 (6.60 ppm). In the soil, lead turns into relatively soluble compounds, carbonate and phosphate, from which it is released due to acidification. When present in higher concentrations it causes numerous physiological, anatomic, morphological and chemical changes (Deng et al., 2004). Cd reaches plants through their roots, but also from the air and above-ground parts of the plant. Its ability to form complexes with Cl - and OH - ions also contributes to this, which leads to greater mobility in the environment and increases the possibility of altering adsorption to cations (Ca 2+ and Zn 2+ ). The increased level of Cd in the plants which were collected near the landfill where waste is burned and next to the highway is probably the result of accumulation which was made possible through the above ground parts of the plants. The content of copper in the flower of the plant Thymus serpyllumm is within the normal limits for herbaceous annual plants and vegetables. Copper can be found in the soil up to 20mg/kg, but it is not a very mobile cation, so it is easily bonded to clay minerals, adsorbed, to form complexes and so is not readily available to plants and so is more frequent in the soil. The results of the determination of the overall content of lead in commercial plant drugs, as well as the content of lead in teas prepared according to the recommendations of the manufacturers, by means of the PSA are shown in Table 8. Content of Pb (μg/g) Pb leached Sample t s (%) Chamomillae flos 0.73-0.81 0.32-0.35 43.20-44.00 Senae folium 1.21-1.64 0.58-0.74 45.12-47.93 Theae folium 1.74-2.37 0.27-0.39 14.28-16.46 Menthae folium 1.18-1.34 0.42-0.48 35.59-36.59 Uvae ursi folium 0.92-1.13 0.27-0.30 25.66-29.34 Table 8. The overall and soluble contents of Pb in herbal drugs and tea mixtures The obtained results indicate that plant-based drugs contain a certain amount of lead, but that the obtained contents are within the limits prescribed for this metal. The content of lead which is released from the plant-based drug into the tea was 3 to 5 times lower than the overall content of this metal. The smallest percentage of the leached lead was found in green tea, which indicates that the migration of lead from this plant-based drug into the tea is the smallest. The lead content in teas depends on how they are prepared and is higher in teas which are prepared as a decoction, and the lowest in those prepared as macerate. 5.6 Using the PSA in the quality control of glass packaging for the food and pharmaceutical industry Glass is a high quality packaging material, which is used in the food and pharmaceutical industry. Packaging, in addition to its basic components, can also contain metals (lead, zinc) as pollutants or as components used to achieve higher quality packaging. Considering the fact that products over a longer period of time, from packaging to use, are in contact with the packaging material, there is the possibility of ion metal migration from the packaging into the product. The international standard (ISO 7086/2) prescribes that the content of the Wide Spectra of Quality Control 230 leached lead from glass packaging cannot exceed the prescribed limits of 5 mg/dm 3 , for small hollow glass and 2.5 mg/dm 3 , for large glass, under prescribed conditions. Table 9 compares the results from a measuring of the contents of soluble lead from glass packaging for the food industry, under prescribed conditions, using different stripping analysis techniques and the AAS technique, as the referential technique prescribed by the standard (Kaličanin et al., 2001a, 2001b, 2001c; 2002). C Pb (μg/dm 3 ) Analytical methods Sample PSA PSA-i R AAS Bottle for fruit juice, 1 dm 3 of volume, colorless 2.20 2.30 1.80 Jar, 1.5 dm 3 of volume, colorless 2.80 2.91 1.80 Jar, 0.72 dm 3 of volume, colorless 1.70 1.82 0.80 Bottle for strong alcoholic drinks, 0.7 dm 3 of volume, of green color 2.70 2.86 2.80 Table 9. Lead contents in the glassware for the food industry extracts by applying the PSA, PSA-i R (potentiometric stripping analysis with constant inverse current in the analytic step) and AAS These results indicate that there is proper agreement between the contents obtained through the stripping techniques and AAS technique as the referential one. Figure 5, shows the content of the leached Pb from various packaging material, which is used in the pharmaceutical industry, during a period of 1, 5 and 7 days. Most of the lead is leached from glass packaging of brown color and of greater volume. According to our research, plastic packaging is more durable to the effects of an acidic medium. Fig. 5. The content of leached lead from packaging for the pharmaceutical industry a) glassware b) plastic and metal, depending on the duration exposure, volume and color of the packaging The Application of the Potentiometric Stripping Analysis to Determine Traces of M(II) Metals (Cu, Zn, Pb and Cd) in Bioinorganic and Similar Materials 231 5.7 The use of the PSA in the quality control of dental-prosthetic material Dental-prosthetic material is very pure material of varying compositions. The same materials can consist of toxic heavy metals (Pb, Cd, Zn, Cu) which can be released under the influence of the corrosive effect of the oral medium or food with a high acidic taste (O'Brien, 2002). During the production phase of prosthetic implants, due to various physical-chemical processes, they are transformed into more stable units, they become less mobile, so that the finished product (metalceramic crown) limited release (Kaličanin & Ajduković, 2008; Kaličanin et al., 2007; Nikolić et al., 2001; Kaličanin & Nikolić, 2008, 2010).The results shown in table 10 indicate that these materials also contain Cu, Zn, Pb and that their traces can also be determined by means of the PSA technique. Sample Cu RSD (%) Zn RSD (%) Pb RSD (%) Dental ceramic 1.98 3.87 1.20 2.83 104.50 1.30 Ceramic color 2.05 1.93 0 .55 4.70 1.25 3.30 Cast alloys 2.60 2.14 215.95 4.39 0.33 10.60 Metal-ceramic crown 3.40 3.13 6.30 7.15 0.65 4.80 Zinc-phosphate cement 1.20 2.80 - - 2.65 1.90 Glass- ionomer cement 0.76 1.50 1.98 2.15 0.35 1.80 Acrylic materials n.d. - 53.05 12.50 4.50 3.80 Hydroxyapatite 33.05 8.50 116.10 15.50 5.70 3.50 Table 10. The content (μg/g) of released copper, zinc and lead from various dental prosthetic materials under the effect of 4% acetic acid, over a period of 24 hours 6. Conclusion The potentiometric stripping analysis is a highly sensitive and highly selective instrumental microanalytic technique for the quantitative determination of the metal ions. This technique can be used to determine low contents of heavy metals (Cu, Zn) and highly toxic metals (Pb and Cd) in samples of various origins Lead can be determined up to levels of 0.65 μg/dm 3 , and cadmium up to 0.10 μg/dm 3 , under the prescribed optimal conditions. PSA fulfills very strict general and specific microanalytic demands: • High sensitivity and proper analytical selectivity • The possibility of determining a large number of elements at the same time • The possibility of the unlimited re-analyses of the same solution • The relatively small instrumentation and the possibility of “on-the-spot” analyses • Lower cost of the instrumentation and exploitation in relation to other techniques. The results of the determination of the content of Cu, Zn, Pb and Cd in the samples of bioinorganic and similar origin, have shown that the PSA technique with oxygen as an oxidant, as the simplest modification that can be done to this technique, can be used in the analysis and quality control of various samples with success. This technique can also be used to analyze: • Clinical-biological material (mineral and soft tissue in vivo and in vitro analyses) • Samples significant in quality control of the environment (water, soil) Wide Spectra of Quality Control 232 • Plant material samples (herbs and aromatic plants, tea mixtures and spices) • Packaging material and packaging for food and pharmaceutical products (glass, ceramics, plastic, metal) • Highly pure bioinorganic material (dental-prosthetic materials) • Beauty products. 7. Acknowledgment Some results presented here are part of projects Nº 45017 and 41018, which have been realized with partial financial support of the Republic of Serbia Ministry of Science and Environmental Protection. We would also like to thank Marta Dimitrijevic for translating the original paper from Serbian into English. 8. References Ahasan, H.A.M.N.; Chowdhury, M.A.J. & Azhar, M.A. (1994). Copper sulphate poisoning. 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A handbook of decomposition methods in analytical chemistry, pp. 122-138, International texbook company, ISBN 0470265019, Edinburgh Brainina, K. & Neyman, E. (1993). Electroanalytical Stripping Methods (Chemical Analysis: A Series of Monographs on Analytical Chemistry and Its Applications), pp. 1-190, Wiley- Interscience, ISBN 9780471595069, New York Brzoska, M.M. & Moniuszko-Jakoniuk, J. (1998). The influence of calcium content in diet on cumulation and toxicity of cadmium in the organism. Archives of Toxicology, Vol. 72, pp. 63-73, ISSN 0340-5761 Cairns, A.M.; Watson, M., Creanor, S.L. & Foye, R.H., (2002). The pH and titrable acidity of a range of diluting drinks and their potential effect on dental erosion. Journal of Dentistry, Vol. 30, pp. 313-7, ISSN 0300-5712 Chapman, T.L. (2008). Genetic Heavy Metal Toxicity: Explaining SIDS, Autism, Tourette's, Alzheimer's and Other Epidemics, pp. 1-119, Universe Inc. Lincoln, ISBN 978-0-595- 48056-2, New York Chobanian, S.J. (1981). Accidental ingestion of liquid zinc chloride: local and systemic effects. Annals of Emergency Medicine, Vol. 10, pp. 91-93, ISSN 0196-0644 The Application of the Potentiometric Stripping Analysis to Determine Traces of M(II) Metals (Cu, Zn, Pb and Cd) in Bioinorganic and Similar Materials 233 Choi, D.; Yokoyama, M. & Koh, J. (1988). Zinc neurotoxicity in cortical cell culture. Neuroscience, Vol. 24, pp. 67-79, ISSN 0306-4522 Danielsson, L.; Jagner, D., Josefson, M. & Westerlund, S. (1981). Computerized potentiometric stripping analysis for the determination of cadmium, lead, copper and zinc in biological materials. Analytica Chimica Acta, Vol. 127, pp. 147-156, ISSN 0003-2670 Deng, H., Ye, Z.H. & Wong, M.H. (2004). Accumulation of lead, zinc, copper and cadmium by 12 wetland species thriwing in metal-contaminated sites in China. Environmental Pollution, Vol. 132, pp. 29-40, ISSN 0269-7491 Ehlen, L.A.; Marshall, T.A., Qian, F., Wefel, J.S. & Warren, J.J. (2008). Acidic beverages increase the risk of in vitro tooth erosion. Nutrition Research Vol. 28, pp. 299–03, ISSN 0271-5317 Florianezyk, B. (1995). Toxic and cancerogenic properties of cadmium. Nowiny Lekarskie, Vol. 64, pp. 737-745, ISSN 0860-7397 Glassware and Glass Ceramic Ware in Contact with Food; Release of Lead and Cadmium, Part. 2: Permissible limits, ISO 7086/2 Gotteland, M.; Araya, M. & Pizarro, F. (2001). Effect of acute copper exposure on gastrointestinal permeability in health volunteers. Digestive Diseases and Sciences, Vol. 46, pp. 1909-1914, ISSN 0163-2116 Goyer, R.A. (1997). Toxic and essential metal interactions. Annual Review of Nutrition, Vol 17, pp. 37-50, ISSN 0199-9885 Goyer, R. & Klaassen, C.D. (1995). Metal Toxicology, pp. 31-45, Academic Press, ISBN 0122943759, San Diego Gulson, B.L. & Gillings, B.R. (1997). Lead exchange in teeth and bone-a pilot study using stable lead isotopes. 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Rapid method for the determination of copper(II) and lead (II) in tap water using a portable potentiometric stripping analyser. Analytica Chimica Acta, Vol. 278, pp. 237-242, ISSN 0003-2670 Jeftović, M. (2001). Zelena riznica, pp. 135-137, Zadužbina Andrejević, ISBN 86-7244-250-4, Beograd Wide Spectra of Quality Control 234 Kaličanin, B. (2006). Zubi, dentalni materijali i teški metali, pp. 7-66, Zadužbina Andrejević, ISBN 86-7244-590-2, Beograd Kaličanin, B. (2009). Determination of very toxic metal — Cadmium in natural water samples. Desalination, Vol. 249, pp. 58-62, ISSN 0011-9164 Kaličanin, B. & Ajduković, Z. (2008). Influence of saliva medium on feeing heavy metal ion from fixed dentures. Science of the Total Environment, Vol. 397, pp. 41-45, ISSN 0048- 9697 Kaličanin, B.; Ajduković, Z., Kostić, M., Najman, S., Savić, V. & Ignjatović, N. (2007). The role of synthetic biomaterials in resorptive alveolar bone regeneration. Hemijska Industrija, Vol. 61, pp. 96-100, ISSN 0367-598X Kaličanin, B.M., Marjanović, N.J. & Suturović, Z.J. (2002). Application of potentiometric stripping analysis with constant inverse curent in the analitic step for determining lead in glassware. Journal of the Serbian Chemical Society, Vol. 67, pp. 213-220, ISSN 0352-5139 Kaličanin, B.M., Marjanović, N.J. & Suturović, Z.J. (2001a). Determination of the soluble lead in the glassware by the potentiometric stripping analysis. Acta Periodica Technologica, Vol. 32, pp. 61-70 ISSN 1450-7188 Kaličanin, B.M., Marjanović, N.J. & Suturović, Z.J. (2001b). The development of a high sensitivity method for the electrochemical determination of soluble lead in glassware. Hemijska industrija, Vol. 55, pp. 407-410, ISSN 0367-598X Kaličanin, B.M. & Nikolić, R. (2010). Copper release from dental prosthetic crowns, dental materials, and human teeth into acetic acid. 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Collection of Czeshosovak Chemical Communications, Vol. 65, pp. 1047-1054, ISSN 0010-0765 The Application of the Potentiometric Stripping Analysis to Determine Traces of M(II) Metals (Cu, Zn, Pb and Cd) in Bioinorganic and Similar Materials 235 Labar, Ch. & Lamberts, L. (1994). Determination of metals in animal tissues by potentiometric stripping analysis without chemical destruction of organic matter. Electrochimica Acta, Vol. 39, pp. 317-325, ISSN 0013-4686 McKenzie, H.A. (1988). Quantitative Trace Analysis of Biological Materials: Principles and Methods for Determination of Trace Elements and Trace Amounts of Some Macro Elemements, pp. 567-785, Elsevier Science Ltd, ISBN 0444809589 Mendil, D., Celik, F., Tuzen, M. & Soylak, M. (2009). Assessment of trace metal levels in some moss and lichen samples collected from near the motorway in Turkey, Journal of Hazardous Materials, Vol. 166, pp. 1344-1350, ISSN 0304-3894 Munoz, E. & Palmero, S. (2006). Determination of heavy metals in honey by potentiometric stripping analysis and using a continuous flow methodology. Food Chemistry, Vol. 94, pp. 478–483, ISSN 0308-8146 Munoz, E. & Palmero, S. (2004). Determination of heavy metals in milk by potentiometric stripping analysis using a home-made flow cell. Food Control, Vol. 15, pp. 635–641, ISSN0956-7135 Nikolić, R., Kaličanin, B. & Nikolić, G. (2004). The determination of soluble lead and soluble cadmium in dental prosthetic materials and teeth by potentiometric stripping analysis. Journal of the Serbian Chemical Society, Vol. 69, pp. 575-580, ISSN 0352-5139 Nikolić, R., Kaličanin, B. & Marjanović, N.J. (2001). Potentiometric stripping analysis of the soluble lead released from dental ceramic materials. Facta Universitatis, series: Physics, Chemistry and Technology, Vol. 2, pp. 159-163, ISSN 0354-4656 O'Brien, W.J. (2002). 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(2006). App lication of gallium film electrode for elimination of copper interference in anodic stripping voltammetry of zinc. Talanta, Vol. 71, pp. 2098-2101, ISSN 0039-9140 Uauy, R., Oliveras, M. & Gonzales, M. (1998). Essentiality of copper in humans. American Journal of Clinical Nutrition, Vol. 67, pp. 952S-959S, ISSN 0002-9165 Vig, E.K. & Hu, H. (2000). Lead toxicity in older adults. Journal of the American Geriatrics Society, Vol. 48, pp. 1501-1506, ISSN 0002-8614 Vydra, F., Stulik, K. & Julakova, E. (1976). Electrochemical Stripping Analysis, pp. 1-260, Ellis Horwood Ltd, ISBN 085312017X Wang, J. (1985). Stripping Analysis, pp. 1-147, VCH Publishers, ISBN: 0895731436, Florida Wide Spectra of Quality Control 236 Walsh, C. T., Sandstead, H.H., Prasad, A.S., Newberne, P.M. & Fraker, P.J. (1994). Zinc: Health effects and research priorities for the 1990s. Environmental Health, Vol. 102, pp. 5-46, ISSN 0091-6765 World Health Organization. Trace elements in human nutrition and helth, Geneva, 1996. 13 Near Infra Red Spectroscopy Ahmed Badr Eldin Sigma Pharmaceutical Corp., Egypt 1. Introduction NIR stands for Near Infrared and refers to the region of light immediately adjacent to the visible range, falling between 750 and 3,000 nanometers (nm = nanometers or 1/1000000000 of a meter) in wavelength. Most organic materials have well defined reflectance or transmittance features at these wavelengths. According to the principles of quantum physics, molecules may only assume discrete energy levels. Similar to the vibrating string of a musical instrument, the vibration of a molecule has a fundamental frequency, or wavelength, as well as a series of overtones. For molecules, the fundamental vibrations involve no change in the center of gravity of the molecule. The spectrum shape for any material is the result of these characteristic fundamentals and overtones. Near-infrared spectra are primarily the result of overtones, whereas there are many fundamentals in the mid and far infrared regions. Since the molecular structure of most compounds is very complex, the resulting spectra are actually the result of many overlapping peaks and valleys. Generally speaking, persons performing NIR analysis must then identify and characterize specific features in the spectra by means of statistical methods. Chemometrics software is designed to accomplish this task. The absorption of NIR radiation by organic molecules is due to overtone and combination bands primarily of O-H, C-H, N-H and C=O groups whose fundamental molecular stretching and bending absorb in the mid-IR region. These overtones are anharmonic, i.e., they do not behave in a simple fashion, making NIR spectra complex and not directly interpretable as in other spectral regions. Below is a graph depicting the prominent absorption bands as they relate to the overtone and combination bands of the fundamental vibrations occurring in the Mid IR region. To understand the types of measurements possible using NIR light, it is useful to understand several general properties of electromagnetic waves, as well as basics of classical molecular and atomic structure. EM radiation, is in the form of waves, and as such, has all the properties of a wave; including wavelength. Figure 1 graph is a typical wave. Wavelength is a distance between two points. Wavelength is particularly important to our discussion as it is closely connected to energy. Wavelength and energy are readily convertible from one to the other when speaking of EM waves. See figure 2 below They are related in the following manner Wide Spectra of Quality Control 238 hc E λ = (1) E = energy, h = Planck's constant (6.626 x 10-27), c = speed of light (2.998 x 1010dm/s), and l = wavelength. Fig. 1. Graph of near-infrared overtone absorptions, peaks and positions Fig. 2. Electromagnetic spectrum [...]... Aberdeen, Scotland, August 19- 23, 199 1, Weinheim, New York, Basel, Cambridge, VCH, 199 2 [4] Burns D A and E W Ciurczak (Eds.), Handbook of Near-Infrared Analysis, (Volume 13 in Practical Spectroscopy Series), Marcel Dekker, Inc., New York, 199 2, pgs 393 - 395 Part 3 Quality Control in Clinics 14 Quality Control in Hospital Bone Banking Eline W Zwitser and Barend J van Royen Department of Orthopaedic Surgery... (Aro&Aho 199 3; Summers and Eisenstein 198 9) Therefore allografts supplied by a bone bank are commonly used instead Allogenic bone exclusively has osteoconductive activity; it serves as an acellular mineralized frame against which newly formed bone gets deposited (Elves and Pratt 197 5; Urist 195 3) Indications for the use of allografts are wide 254 Wide Spectra of Quality Control and include treatment of bone... heads (Zwitser et al 20 09; Sugihara et al 199 9) Therefore, we recommend the routine histopathological evaluation of all femoral heads removed during elective total hip arthroplasty as a tool for quality control The costperformance ratio of routine histopathological evaluation is discussed in literature (Kocher et al 2000; Meding et al 2000; Lawrence et al 199 9; Campbell et al 199 7) Therefore we performed... Introduction The use of allogenic bone transplantation is nowadays a standard orthopaedic procedure It is widely used for reconstruction of bone defects that arise from trauma (Friedlaender 198 7), infection, resection of bone tumours (Mankin et al 199 6) or it is used in spinal fusion (Raizman et al 20 09) and as impaction grafting in revision of total joint arthroplasty (Slooff et al 199 6) Although autologous... stretch/C-H deformation C-H stretch first overtone 1 695 CH2 bend second overtone C-H stretch first overtone 1705 C-H stretch/C-C stretch combination C-H stretch first overtone 1725 C-H combination S-H stretch first overtone 1740 Sym C-N-C stretch overtone Table 1 Wavelength (nm) 1820 1860 190 0 190 8 192 0 193 0 194 0 195 0 196 0 198 0 199 0 2030 2050 2060 2060 2070 2070 2 090 2100 2100 2140 2170 2180 2200 2270 2280 2300... Continuing addition of protons, neutrons, and electrons would produce atoms in the numeric sequence listed in the periodic chart of the elements 240 Wide Spectra of Quality Control Molecules are a group of atoms which have combined together to form a chemical compound Molecules are simply substances made of several atoms of similar or different elements Chemicals made of different types of atoms may have... (MacEwen 190 9) In the following decades the technique of transplantation of large allografts in septic arthritis and osteomyelitis was further developed and popularised by a German surgeon He used fresh long bones of amputated limbs and used them as osteoarticular allografts with a reported success rate of 50% (Lexer 190 8, 192 5) Later, in 192 9 Alexander Fleming discovered the antibacterial properties of penicillium... bone banking 252 Wide Spectra of Quality Control procedure and protocol This constantly updated protocol is of the utmost importance in order to prevent the transmission of infectious diseases Because of the potential risk of transmission of diseases from donor to recipient we performed routine histological examination in the screening protocol We found a relatively high percentage of pathological conditions... significant problem in orthopaedic surgery (Slooff et al 199 6) The migration of implants during loosening and procedures to remove the prosthesis and cement during revision induce significant bone destruction, resulting in enlargement of the acetabulum and widening of the femoral medullary cavity Because of the magnitude of the loss of bone, allograft bone is often needed, at revision, to provide stability... extremity (Parrish 197 3, Mankin et al 197 6) In a series of 19 allograft replacements for osseous malignancies satisfactory results were reported in 75% of patients In the largest series of two hundred lower extremity osteoarticular allografts performed between 197 6 and 199 7 for malignant bone tumours, results were diminished by radiation and chemotherapy (Hazan et al 2001) In the first century of bone transplantation . pp. 190 9- 191 4, ISSN 0163-2116 Goyer, R.A. ( 199 7). Toxic and essential metal interactions. Annual Review of Nutrition, Vol 17, pp. 37-50, ISSN 0 199 -98 85 Goyer, R. & Klaassen, C.D. ( 199 5) pp. 2 098 -2101, ISSN 00 39- 9140 Uauy, R., Oliveras, M. & Gonzales, M. ( 199 8). Essentiality of copper in humans. American Journal of Clinical Nutrition, Vol. 67, pp. 95 2S -95 9S, ISSN 0002 -91 65. ISBN 97 80471 595 0 69, New York Brzoska, M.M. & Moniuszko-Jakoniuk, J. ( 199 8). The influence of calcium content in diet on cumulation and toxicity of cadmium in the organism. Archives of Toxicology,

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