Abstract
Previous studies suggest that different copper species formed in saliva have different reactivity in chemical reactions that may be associated with perception of metallic sensation occurring in the oral cavity. This study was performed to understand copper speciation in human saliva, which will help to understand the perception mechanism of metallic taste. Saliva samples were treated with CuSO4·5H2O at the levels of 0, 2.5, 10, 20, or 40 mg/L as Cu in vitro. Also saliva is collected before and after drinking 20 mL of 0, 2.5, and 5 mg/L copper in water (in vivo treatment). Copper speciation was operationally determined based on apparent molecular size using ultrafiltration coupled with inductively coupled plasma mass spectrometry. For in vitro copper treatment, 50–70% of copper was soluble at Cu ≤ 10 mg/L, whereas 60–70% of copper was in complex or insoluble form at Cu > 20 mg/L. For in vivo copper treatment, 90–95% of copper was soluble in saliva. These results suggest that copper is in the soluble unbound form in saliva at low concentrations. At higher concentrations, copper either becomes insoluble or binds with salivary components.
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Dietrich A, Glindemann D, Pizzaro F, Gidi V, Olivares M, Araya M, Camper A, Duncan S, Dwyer S, Whelton A, Younos T, Subramanian S, Burlingame G, Khiari D, Edwards M (2004) Health and aesthetic impacts of copper corrosion on drinking water. Water Sci Technol 49:55–62
Edwards M, Spragues N (2004) Organic matter and copper corrosion byproduct release: a mechanistic study. Corrosion Sci 43:1–18
National tap water quality database (2005) Environmental Working Group (EWG), Washington DC. http://www.ewg.org/tapwater/contaminants/contaminant.php?contamcode=1022. Assessed 30 June 2009
Desphande SS (2002) Handbook of food toxicology. Marcel Dekker Inc, New York, pp 177–179
National Research Council (NRC) (2000) Copper in drinking water. National Academic Press, Washington DC
Fizgerald DJ (1998) Safety guidelines for copper in water. Am J Clin Nutr 67(suppl):1098s–1102s
Cockell KA, Bertinato J, L’Abbe MR (2008) Regulatory frameworks of copper considering chronic exposures of the population. Am J Clin Nutr 88(Suppl):863S–866S
Araya M, Koletzko B, Uauy R (2003) Copper deficiency and excess in infancy: developing a research agenda. J Pediatr Gastroenterol Nutr 37:422–429
Zacarias I, Yanez CG, Araya M, Oraka C, Olivares M, Uauy R (2001) Determination of the taste threshold of copper in water. Chem Senses 26:85–89
Beguin-Bruhin Y, Escher F, Roth H, Solms J (1983) Threshold concentration of copper in drinking water. Lebensm Wiss 16:22–26
Cuppett JD, Duncan SE, Dietrich AD (2006) Evaluation of copper speciation and water quality factors that affect aqueous copper tasting response. Chem Sense 31:689–697
Epke EM, Lawless HT (2007) Retronasal smell and detection thresholds of iron and copper salts. Physiol Behav 92:487–489
Zoeteman BCJ (1980) Sensory assessment of water quality. Pergamon Press, Oxford
Dietrich A (2008) The many flavors of drinking water. Water Tech 31 http://www.warwas.com/documents/themanyflavorsofdrinkingwater.pdf. Assessed 5 January 2009
Pohl P, Sergiel I (2009) Evaluation of the total content and the operationally defined species of copper in beers and wines. J Agric Food Chem 57:9378–9384
Chapman KW, Lawless HT (2004) Correlation of instrumental measures of saliva turbidity and perceived astringency of metallic salts. 2004 IFT annual meeting abstract archive. 83G-6. http://ift.confex.com/ift/2004/teleprogram/meeting_2004.htm. Accessed 24 September 2007
Riera CE, Vogel SA, Simon SA, Coutre JI (2007) Artificial sweeteners and salts producing a metallic taste sensation activate TRPV1 receptors. Am J Phys Reg Int Com Physiol 293:R626–R634
Hong JH, Duncan SE, Dietrich AM, O’keefe SF, Eigel WN, Mallikarjunan K (2009) Interaction of copper and human salivary proteins. J Agric Food Chem 57:6967–6975
Hong JH, Duncan SE, Dietrich AM, O’Keefe SF (2009) Ultrafiltration as a tool to study binding of copper to salivary proteins. Food Chem 113:180–184
Hong JH, Duncan SE, Dietrich AM (2010) Identification of temporal copper sensation and effect of pH on sensory perception of copper. Food Qual Pref 21:132–139
Tenovuo JO (1989) Human saliva: clinical chemistry and microbiology, vol I. CRC Press Inc, Boca Raton
Dietrich A, Cuppett J, Edwards M, Powers K, Duncan S, Bosch D, Klewczyk E (2005) Corrosion of copper plumbing and its effects on consumer health and economics. In: Proceedings of NSF Design, manufacture, and industrial innovation (DMII) grantee conference. NSF, Washington DC, pp 1–14
Argarwal RP, Henkin RI (1987) Metal binding characteristics of human salivary and porcine pancreatic amylase. J Biol Chem 262:2568–2575
Brewer D, Lajoie G (2000) Evaluation of the metal binding properties of the histidine-rich antimicrobial peptides histatin 3 and 5 by electrospray ionization mass spectrometry. Rapid Comm Mass Spec 14:1736–1745
Gusman H, Lendemann U, Grogan J, Troxler RF, Oppenheim FG (2001) Is salivary histatin 5 a metallopeptide? Biochim Biophys Acta 1545:86–95
Mueller HJ (1983) The binding of corroded metallic ions to salivary-type proteins. Biomaterials 4:66–72
Shatzman AR, Henkin RI (1980) Metal-binding characteristics of the parotid salivary protein gustin. Biochim Biophys Acta 623:107–108
Mueller HJ (1985) Binding of corroded ions to human saliva. Biomaterials 6:146–149
Mueller HJ (1987) The effects of a human salivary dialysate upon ionic release and electrochemical corrosion of a copper-aluminium alloy. J Electrochem Soc 134:575–580
McKinnon AJ, Scollary GR (1997) Size fractionation of metals in wine using ultrafiltration. Talanta 44:1649–1658
Karadjova I, Izgi B, Gucer S (2000) Fractionation and speciation of Cu, Zn and Fe in wine samples by atomic absorption spectrometry. Sperctrochim Acta Part B 57:711–717
Francis CA, Hector MP, Proctor GB (2000) Precipitation of specific proteins by freeze-thawing of human saliva. Arch Oral Biol 45:601–606
Hoffmann MR, Yost EC, Eisenreich SJ, Maier WJ (1981) Characterization of soluble and colloidal phase metal complexes in river water by ultrafiltration. A mass-balance approach. Environ Sci Technol 15:655–661
Copeland RA (1994) Methods for protein quantitation. In: Copeland RA (ed) Methods for protein analysis: a practical guide to laboratory protocols, Chap 3. Chapman and Hall, New York, pp 39–58
Millipore Cooperation. Protein concentration and sample preparation. (2009) http://www.millipore.com/immunodetection/id3/concentration. Accessed 11 November 2009
Kilic Z, Acar O, Ulasan M, Ilim M (2002) Determination of lead, copper, zinc, magnesium, calcium and iron in fresh eggs by atomic absorption spectrometry. Food Chem 76:107–116
APHA, AWWA, WEF (1998) Standard Methods for the Examination of Water and Wastewater, 20th edn. Washington DC
Chicharro JL, Serrano V, Urena R, Gutierrez AM, Carvajal A, Fernandez-Hernando P, Lucia A (1999) Trace elements and electrolytes in human resting mixed saliva after exercise. Br J Sports Med 33:204–207
Vaughan M, Balnee AD, Templeton DM (1991) Multielement analysis of biological samples by inductively coupled plasma-mass spectrometry. II. Rapid survey method for profiling trace elements in body fluids. Clin Chem 37:210–215
Menegário AA, Packer AP, Giné MF (2001) Determination of Ba, Cd, Cu, Pb and Zn in saliva by isotope dilution direct injection inductively coupled plasma mass spectrometry. Analyst 126:1363–1366
Grahammer P, Hiller KA, Retinger T, Schmalz G (2004) Metal content of saliva of patients with and without metal restoration. Clin Oral Invest 8:238–242
Jenzano JW, Hogan SL, Noyes CM, Featherstone GL, Lundbald RL (1986) Comparison of five techniques for the determination of protein concentration in mixed human saliva. Anal Biochem 159:370–376
Kallithraka S, Bakker J, Clifford MN (1998) Evidence that salivary proteins are involved in astringency. J Sensory Studies 13:29–43
Sarni-Manchado P, Cheynier V, Moutounet MJ (1999) Interactions of grape seed tannins with salivary proteins. J Agric Food Chem 47:42–47
Sarni-Manchado P, Canals-Bosch J, Mazerolles G, Cheynier V (2008) Influence of the glycosylation of human salivary proline-rich proteins on their interactions with condensed tannins. J Agric Food Chem 56:9563–9569
Howe KJ, Clark MM (2002) Fouling of microfiltration and ultrafiltration membranes by natural waters. Environ Sci Technol 36:3571–3576
McNeill LS, Edwards M (2004) Importance of Pb and Cu particulate species for corrosion control. J Environ Eng 130:136–144
Millipore Cooperation. Amicon ultra-4 centrifugal devices user guide (2009) http://www.millipore.com/userguides/tech1/pr02843. Accessed 11 Nov 2009
Wu AM, Csako G, Herp A (1994) Structure, biosynthesis, and function of salivary mucins. Mol Cell Biochem 137:39–55
Minaguchi K, Bennick A (1989) Genetics of human salivary proteins. J Dental Res 68:2–15
Glindemann D, Dietrich A, Staerk H, Kuschk P (2006) The smell of touched or pickled iron is not Fe. Ang Chem Int Ed 45:7006–7009
Epke EM, McClure ST, Lawless HT (2009) Effects of nasal occlusion and oral contact on perception of metallic taste from metal salts. Food Qual Pref 20:133–137
Jensen JN (2003) A problem-solving approach to aquatic chemistry. Wiley, Hoboken
Lim J, Lawless HT (2005) Oral sensations from iron and copper sulfate. Physiol Behav 85:308–313
Acknowledgments
This material is based upon work supported by the National Science Foundation under Grant No. 0329474. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation. The authors thank Mr. Jeffrey Parks in Department of Civil and Environmental Engineering for ICP-MS analysis of copper.
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Hong, J.H., Duncan, S.E., Dietrich, A.M. et al. Evaluation of the operationally defined soluble, insoluble, and complexing copper consumed through drinking water in human saliva. Eur Food Res Technol 231, 977–984 (2010). https://doi.org/10.1007/s00217-010-1352-1
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DOI: https://doi.org/10.1007/s00217-010-1352-1