Determination of silver in personal care nanoproducts and effects on dermal exposure

  • Nootcharin Wasukan
  • Sujittra SrisungEmail author
  • Kornphimol Kulthong
  • Suwimon Boonrungsiman
  • Rawiwan ManiratanachoteEmail author
Research Paper


Silver (Ag) is one of the widely used nanomaterials in cosmetics, personal care, and household products. This research aimed to investigate the Ag concentration contained in 20 commercial nanoproducts using a simple and reliable procedure. The exposure and adverse effects of a single topical application of Ag on the skin were also evaluated. Herein, we demonstrated that the technique of wet acid digestion, extraction and detection of Ag with graphite furnace absorption spectrometry were effective for any and all nanoproduct matrices. The Ag morphology was characterized by scanning and transmission electron microscopy equipped with energy-dispersive x-ray spectroscopy. Penetration of Ag was evaluated using a polyethersulfone (PES) membrane through a Franz cell and reconstructed human epidermis (RhE) tissue. A skin irritation test was performed on RhE, an acceptable in vitro model which was in compliance with OECD test guideline 439. The results showed that the initial Ag concentration in the tested nanoproducts ranged between 0.0058 and 94 µg/g. However, particulate Ag was only found in two products, both of a liquid formulation. Silver penetration through a PES membrane (0.12–53 % by weight) was weakly correlated with the initial Ag concentration in each sample, but more so to the product formulation. The liquid products demonstrated the highest percent of average Ag penetration, followed by the semi-solid and solid formulations, respectively. In contrast, neither any Ag diffusion from these products into the RhE tissue nor any irritation or toxicity was detected. This study suggests a screening method to evaluate the Ag level in products and their potential adverse effects on the skin that could be incorporated as a part of risk assessment for nanotechnology products.


Exposure Nanoproducts Penetration Silver Skin irritation Health effects 



This project was financially supported by Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA), and Department of Chemistry, Faculty of Science, Srinakharinwirot University, Thailand. Nootcharin Wasukan received Capital Projects TGIST Scholarship (Grant No. TG-55-17-55-055D) from NSTDA. We acknowledge Prof. Harald F. Krug (EMPA, Swiss Federal Laboratories for Materials Testing and Technology, Switzerland) for suggestions on the first draft of this manuscript. The authors thank Dr. Robert Butcher (Chulalongkorn University, Thailand) for comments and English language review.

Compliance with ethical standards

Conflict of Interest

The authors claim no conflict of interest.

Supplementary material

11051_2015_3220_MOESM1_ESM.doc (1.4 mb)
Supplementary material 1 (DOC 1444 kb)


  1. Chattaraj SC, Swarbrick J, Kanfer I (1995) A simple diffusion cell to monitor drug release from semi-solid dosage forms. Int J Pharm 120:119–124CrossRefGoogle Scholar
  2. Chen X, Schluesener HJ (2008) Nanosilver: a nanoproduct in medical application. Toxicol Lett 176:1–12CrossRefGoogle Scholar
  3. Chung IS, Lee MY, Shin DH, Jung HR (2010) Three systemic argyria cases after ingestion of colloidal silver solution. Int J Dermatol 49:1175–1177CrossRefGoogle Scholar
  4. Ciaralli L, Giordano R, Cassina S, Sepe A, Costantini S (1996) Determination of chromium and nickel in commercial foam bath products by ETA-AAS. Ist Super di Sanita 32:381–385Google Scholar
  5. Dastjerdi R, Montazer M (2010) A review on the application of inorganic nano-structured materials in the modification of textiles: focus on anti-microbial properties. Colloids Surf, B 79:5–18CrossRefGoogle Scholar
  6. Drake PL, Hazelwood KJ (2005) Exposure-related health effects of silver and silver compounds: a review. Ann Occup Hyg 49:575–585CrossRefGoogle Scholar
  7. EPA (2012) 2012 Edition of the drinking water standards and health advisories. Information on the web-site: Accessed 10 Apr 2012
  8. Fubini B, Ghiazza M, Fenoglio I (2010) Physico-chemical features of engineered nanoparticles relevant to their toxicity. Nanotoxicology 4:347–363CrossRefGoogle Scholar
  9. Gabbanini S, Matera R, Beltramini C, Minghetti A, Valgimigli L (2010) Analysis of in vitro release through reconstructed human epidermis and synthetic membranes of multi-vitamins from cosmetic formulations. J Pharm Biomed Anal 52:461–467CrossRefGoogle Scholar
  10. Garcias-Ladaria J, Hernandez-Bel P, Torregrosa-Calatayud JL, Martínez-Aparicio A (2013) Argiria cutánea localizada. A propósito de 2 casos. Actas Dermosifiliogr 104:254–255CrossRefGoogle Scholar
  11. Geiss O, Cascio C, Gilliland D, Franchini F, Barrero-Moreno J (2013) Size and mass determination of silver nanoparticles in an aqueousmatrix using asymmetric flow field flow fractionation coupled to inductively coupled plasma mass spectrometer andultraviolet–visible detectors. J Chromatogr A 1321:100–108CrossRefGoogle Scholar
  12. Hansen SF, Michelson ES, Kamper A, Borling P, Stuer-Lauridsen F, Baun A (2008) Categorization framework to aid exposure assessment of nanomaterials in consumer products. Ecotoxicology 17:438–447CrossRefGoogle Scholar
  13. Henkler F, Tralau T, Tentschert J, Kneuer C, Haase A, Platzek T, Luch A, Götz ME (2012) Risk assessment of nanomaterials in cosmetics: a European union perspective. Arch Toxicol 86:1641–1646CrossRefGoogle Scholar
  14. Ilić V, Šaponjić Z, Vodnik V, Potkonjak B, Jovančić P, Nedeljković J, Radetić M (2009) The influence of silver content on antimicrobial activity and color of cotton fabrics functionalized with Ag nanoparticles. Carbohydr Polym 78:564–569CrossRefGoogle Scholar
  15. Jiang JK, Oberdorster G, Biswas P (2009) Characterization of size, surface charge and agglomeration state of nanoparticle dispersions for toxicological studies. J Nanopart Res 11:77–89CrossRefGoogle Scholar
  16. Lademann J, Otberg N, Jacobi U, Hoffman RM, Blume-Peytavi U (2005) Follicular penetration and targeting. J Investig Dermatol Symp Proc 10:301–303CrossRefGoogle Scholar
  17. Larese FF, D’Agostin F, Crosera M, Adamib G, Renzi N, Bovenzi M, Maina G (2009) Human skin penetration of silver nanoparticles through intact and damaged skin. Toxicology 255:33–37CrossRefGoogle Scholar
  18. Lekki J, Stachura Z, Dabros W, Stachura J, Menzel F, Reinert T, Butz T, Pallon Jan LU, Gontier E, Ynsa MD, Moretto P, Kertesz Z, Szikszai Z, Kiss AZ (2007) On the follicular pathway of percutaneous uptake of nanoparticles: ion microscopy and autoradiography studies. Nucl Instrum Meth Phys Res B 260:174–177CrossRefGoogle Scholar
  19. Loeschner K, Navratilova J, Legros S, Wagner S, Grombe R, Snell J, von der Kammer F, Larsen EH (2013) Optimization and evaluation of asymmetric flow field-flow fractionation of silver nanoparticles. J Chromatogr 1272:116–125CrossRefGoogle Scholar
  20. McKenna JK, Hull CM, Zone JJ (2003) Argyria associated with colloidal silver supplementation. Int J Dermatol 42:549CrossRefGoogle Scholar
  21. Monteiro-Riviere NA, Inman AO, Snider TH, Blank JA, Hobson DW (1997) Comparison of an in vitro skin model to normal human skin for dermatological research. Microsc Res Tech 37:172–179CrossRefGoogle Scholar
  22. NANOTEC (2012) The nanosafety and ethics strategic plan (2012–2016). Information on the web-site: Accessed 20 Feb 2012
  23. Nowack B, Krug HF, Height M (2011) 120 Years of nanosilver history: implications for policy makers. Environ Sci Technol 45:1177–1183CrossRefGoogle Scholar
  24. OSHA (2013) OSHA fact sheet: working safely with nanomaterials US department of labor-occupational safety and health administration. Information on the web-site: Accessed 15 Jan 2013
  25. Otto A, du Plessis J, Wiechers JW (2009) Formulation effects of topical emulsions on transdermal and dermal delivery. Int J Cosmet Sci 31:1–19CrossRefGoogle Scholar
  26. Ponec M, Boelsma E, Weerheim A, Mulder A, Bouwstra J, Mommaas M (2000) Lipid and ultrastructural characterization of reconstructed skin models. Int J Pharm 203:211–225CrossRefGoogle Scholar
  27. Rancan F, Gao Q, Graf C, Troppens S, Hadam S, Hackbarth S, Kembuan C, Blume-Peytavi U, Ru¨hl E, Lademann J, Vogt A (2012) Skin penetration and cellular uptake of amorphous silica nanoparticles with variable size, surface functionalization and colloidal stability. ACS Nano 6:6829–6842CrossRefGoogle Scholar
  28. Ryman-Rasmussen JP, Riviere JE, Monteire-Riviere NA (2006) Penetration of intact skin by quantum dots with diverse physicochemical properties. Toxicol Sci 91:159–165CrossRefGoogle Scholar
  29. Salata OV (2004) Applications of nanoparticles in biology and medicine. J Nanobiotechnol 2:1–6CrossRefGoogle Scholar
  30. Samberg ME, Oldenburg SJ, Monteiro-Riviere NA (2010) Evaluation of silver nanoparticle toxicity in skin in vivo and keratinocytes in vitro. Environ Health Perspect 118:407–413CrossRefGoogle Scholar
  31. SCCS (2012) Guidance on the safety assessment of nanomaterials in cosmetics SCCS/1484/12. Information on the web-site: Accessed 20 Jan 2012
  32. Spielmann H, Hoffmann S, Liebsch M, Botham P, Fentem JH, Eskes C, Roguet R, Cotovio J, Cole T, Worth A, Heylings J, Jones P, Robles C, Kandárová H, Gamer A, Remmele M, Curren R, Raabe H, Cockshott A, Gerner I, Zuang V (2007) The ECVAM international validation study on in vitro tests for acute skin irritation: report on the validity of the EPISKIN and EpiDerm assays and on the skin integrity function test. Altern Lab Anim 35:559–601Google Scholar
  33. Toll R, Jacobi U, Richter H, Lademann J, Schaefer H, Blume-Peytavi U (2004) Penetration profile of microspheres in follicular targeting of terminal hair follicles. J Invest Dermatol 123:168–176CrossRefGoogle Scholar
  34. Tulve NS, Stefaniak AB, Vance ME, Rogers K, Mwilu S, LeBouf RF, Schwegler-Berry D, Willis R, Thomas TA, Marr LC (2015) Characterization of silver nanoparticles in selected consumer products and its relevance for predicting children’s potential exposures. Int J Hyg Environ Health 218:345–357CrossRefGoogle Scholar
  35. U.S. FDA (2014) Guidance for industry: Safety of nanomaterials in cosmetic products. Information on the web-site: Accessed 9 June 2014
  36. Wilkinson SC, Maas WJ, Nielsen JB, Greaves LC, van de Sandt JJ, Williams FM (2006) Interactions of skin thickness and physicochemical properties of test compounds in percutaneous penetration studies. Int Arch Occup Environ Health 79:405–413CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Nootcharin Wasukan
    • 1
    • 2
  • Sujittra Srisung
    • 2
    Email author
  • Kornphimol Kulthong
    • 1
  • Suwimon Boonrungsiman
    • 1
  • Rawiwan Maniratanachote
    • 1
    Email author
  1. 1.National Nanotechnology CenterNational Science and Technology Development Agency (NSTDA)Khlong LuangThailand
  2. 2.Department of Chemistry, Faculty of ScienceSrinakharinwirot UniversityWattana District, BangkokThailand

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