Abstract
A comparative assessment of the 48-h acute toxicity of aqueous nanoparticles synthesized using the same methodology, including Au, Ag, and Ag–Au bimetallic nanoparticles, was conducted to determine their ecological effect in freshwater environments through the use of Daphnia magna, using their mortality as a toxicological endpoint. D. magna are one of the standard organisms used for ecotoxicity studies due to their sensitivity to chemical toxicants. Particle suspensions used in toxicity testing were well-characterized through a combination of absorbance measurements, atomic force or electron microscopy, flame atomic absorption spectrometry, and dynamic light scattering to determine composition, aggregation state, and particle size. The toxicity of all nanoparticles tested was found to be dose and composition dependent. The concentration of Au nanoparticles that killed 50% of the test organisms (LC50) ranged from 65–75 mg/L. In addition, three different sized Ag nanoparticles (diameters = 36, 52, and 66 nm) were studied to analyze the toxicological effects of particle size on D. magna; however, it was found that toxicity was not a function of size and ranged from 3–4 μg/L for all three sets of Ag nanoparticles tested. This was possibly due to the large degree of aggregation when these nanoparticles were suspended in standard synthetic freshwater. Moreover, the LC50 values for Ag–Au bimetallic nanoparticles were found to be between that of Ag and Au but much closer to that of Ag. The bimetallic particles containing 80% Ag and 20% Au were found to have a significantly lower toxicity to Daphnia (LC50 of 15 μg/L) compared to Ag nanoparticles, while the toxicity of the nanoparticles containing 20% Ag and 80% Au was greater than expected at 12 μg/L. The comparison results confirm that Ag nanoparticles were much more toxic than Au nanoparticles, and that the introduction of gold into silver nanoparticles may lower their environmental impact by lowering the amount of Ag which is bioavailable.
Similar content being viewed by others
References
Baraton MI, Merhari L (2004) Nanoparticles-based chemical gas sensors for outdoor air quality monitoring microstations. Mater Sci Eng B Solid State Mater Adv Technol 112:206–213
Lim JK, Joo SW (2006) Gold nanoparticle-based pH sensor in highly alkaline region at pH > 11: surface-enhanced Raman scattering study. Appl Spectrosc 60:847–852
Bishnoi SW, Rozell CJ, Levin CS, Gheith MK, Johnson BR, Johnson DH, Halas NJ (2006) All-optical nanoscale pH meter. Nano Lett 6:1687–1692
Jayakumar R, Chennazhi KP, Muzzarelli RAA, Tamura H, Nair SV, Selvamurugan N (2010) Chitosan conjugated DNA nanoparticles in gene therapy. Carbohydrate Polymers 79:1–8
Taton TA, Mirkin CA, Letsinger RL (2000) Scanometric DNA array detection with nanoparticle probes. Science 289:1757–1760
Cai C, Bakowsky U, Rytting E, Schaper AK, Kissel T (2008) Charged nanoparticles as protein delivery systems: a feasibility study using lysozyme as model protein. Eur J Pharm Biopharm 69:31–42
Grubisha DS, Lipert RJ, Park H-Y, Driskell J, Porter MD (2003) Femtomolar detection of prostate-specific antigen: an immunoassay based on surface-enhanced Raman scattering and immunogold labels. Anal Chem 75:5936–5943
Thaxton CS, Georganopoulou DG, Mirkin CA (2006) Gold nanoparticle probes for the detection of nucleic acid targets. Clin Chim Acta 363:120–126
Yanez-Sedeno P, Pingarron JM (2005) Gold nanoparticle-based electrochemical biosensors. Anal Bioanal Chem 382:884–886
Van Hyning DL, Zukoski CF (1998) Formation mechanisms and aggregation behavior of borohydride reduced silver particles. Langmuir 14:7034–7046
Adair JH, Suvaci E (2000) Morphological control of particles. Curr opin colloid interface sci 5:160–167
Jana NR, Gearheart L, Murphy CJ (2001) Evidence for seed-mediated nucleation in the chemical reduction of gold salts to gold nanoparticles. Chem Mater 13:2313–2322
Velikov KP, Zegers GE, van Blaaderen A (2003) Synthesis and characterization of large colloidal silver particles. Langmuir 19:1384–1389
D'Souza L, Suchopar A, Richards RM (2004) In situ approaches to establish colloidal growth kinetics. J Colloid Interface Sci 279:458–463
Tiede K, Hassellov M, Breitbarth E, Chaudhry Q, Boxall ABA (2009) Considerations for environmental fate and ecotoxicity testing to support environmental risk assessments for engineered nanoparticles. J Chromatogr A 1216:503–509
Ostrowski A, Martin T, Conti J, Hurt I, Harthorn B (2009) Nanotoxicology: characterizing the scientific literature, 2000–2007. J Nanopart Res 11:251–257
Wijnhoven SWP, Peijnenburg W, Herberts CA, Hagens WI, Oomen AG, Heugens EHW, Roszek B, Bisschops J, Gosens I, Van de Meent D, Dekkers S, De Jong WH, Van Zijverden M, Sips A, Geertsma RE (2009) Nano-silver—a review of available data and knowledge gaps in human and environmental risk assessment. Nanotoxicology 3:109–U178
Stevens KNJ, Crespo-Biel O, van den Bosch EEM, Dias AA, Knetsch MLW, Aldenhoff YBJ, van der Veen FH, Maessen JG, Stobberingh EE, Koole LH (2009) The relationship between the antimicrobial effect of catheter coatings containing silver nanoparticles and the coagulation of contacting blood. Biomaterials 30:3682–3690
Prema P, Raju R (2009) Fabrication and characterization of silver nanoparticle and its potential antibacterial activity. Biotechnol Bioprocess Eng 14:842–847
Gao J, Youn S, Hovsepyan A, Llaneza VL, Wang Y, Bitton G, Bonzongo JCJ (2009) Dispersion and toxicity of selected manufactured nanomaterials in natural river water samples: effects of water chemical composition. Environ Sci Technol 43:3322–3328
Benn TM, Westerhoff P (2008) Nanoparticle silver released into water from commercially available sock fabrics. Environ Sci Technol 42:4133–4139
Shahverdi AR, Fakhimi A, Shahverdi HR, Minaian S (2007) Synthesis and effect of silver nanoparticles on the antibacterial activity of different antibiotics against Staphylococcus aureus and Escherichia coli. Nanomed Nanotechnol Biol Med 3:168–171
Simon-Deckers A, Brun E, Gouget B, Carriere M, Sicard-Roselli C (2008) Impact of gold nanoparticles combined to X-ray irradiation on bacteria. Gold Bulletin 41:187–194
Mueller NC, Nowack B (2008) Exposure modeling of engineered nanoparticles in the environment. Environ Sci Technol 42:4447–4453
Griffitt RJ, Luo J, Gao J, Bonzongo JC, Barber DS (2008) Effects of particle composition and species on toxicity of metallic nanomaterials in aquatic organisms. Environ Toxicol Chem 27:1972–1978
Asharani PV, Wu YL, Gong ZY, Valiyaveettil S (2008) Toxicity of silver nanoparticles in zebrafish models. Nanotechnology 19:8
Glover CN, Wood CM (2005) Accumulation and elimination of silver in Daphnia magna and the effect of natural organic matter. Aquat Toxicol 73:406–417
Glover CN, Wood CM (2004) Physiological interactions of silver and humic substances in Daphnia magna: effects on reproduction and silver accumulation following an acute silver challenge. Comp Biochem Physiol C Toxicol Pharmacol 139:273–280
AshaRani PV, Low Kah Mun G, Hande MP, Valiyaveettil S (2008) Cytotoxicity and genotoxicity of silver nanoparticles in human cells. ACS Nano 3:279–290
Choi O, Hu ZQ (2008) Size dependent and reactive oxygen species related nanosilver toxicity to nitrifying bacteria. Environ Sci Technol 42:4583–4588
Carlson C, Hussain SM, Schrand AM, K. Braydich-Stolle L, Hess KL, Jones RL, Schlager JJ (2008) Unique cellular interaction of silver nanoparticles: size-dependent generation of reactive oxygen species. J Phys Chem B 112:13608–13619
Morones JR, Elechiguerra JL, Camacho A, Holt K, Kouri JB, Ramirez JT, Yacaman MJ (2005) The bactericidal effect of silver nanoparticles. Nanotechnology 16:2346–2353
Oberdorster G, Oberdorster E, Oberdorster J (2005) Nanotoxicology: an emerging discipline evolving from studies of ultrafine particles. Environ Health Perspect 113:823–839
AshaRani PV, Mun GLK, Hande MP, Valiyaveettil S (2009) Cytotoxicity and genotoxicity of silver nanoparticles in human cells. ACS Nano 3:279–290
ASTM Standard E1193 - 97, 2004 "Standard Guide for Conducting Daphnia magna Life-Cycle Toxicity Tests". (West Conshohocken, PA: ASTM International)
EPA 2002 Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms. ed Agency U S E P
OECD 1984 Daphnia sp., acute immobilisation test and reproduction test. In: Part I - the 24 h EC 50 acute immobilisation test, pp 2 - 5
Lovern SB, Owen HA, Klaper R (2008) Electron microscopy of gold nanoparticle intake in the gut of Daphnia magna. Nanotoxicology 2:43–48
Lovern SB, Klaper R (2006) Daphnia magna mortality when exposed to titanium dioxide and fullerene (C-60) nanoparticles. Environ Toxicol Chem 25:1132–1137
Zhu XS, Zhu L, Chen YS, Tian SY (2009) Acute toxicities of six manufactured nanomaterial suspensions to Daphnia magna. J Nanopart Res 11:67–75
Murdock RC, Braydich-Stolle L, Schrand AM, Schlager JJ, Hussain SM (2008) Characterization of Nanomaterial Dispersion in Solution Prior to In Vitro Exposure Using Dynamic Light Scattering Technique. Toxicol Sci 101:239–253
Ahamed M, Karns M, Goodson M, Rowe J, Hussain SM, Schlager JJ, Hong YL (2008) DNA damage response to different surface chemistry of silver nanoparticles in mammalian cells. Toxicol Appl Pharmacol 233:404–410
Thevenot P, Cho J, Wavhal D, Timmons RB, Tang LP (2008) Surface chemistry influences cancer killing effect of TiO2 nanoparticles. Nanomed Nanotechnol Biol Med 4:226–236
Kora AJ, Manjusha R, Arunachalam J (2009) Superior bactericidal activity of SDS capped silver nanoparticles: synthesis and characterization. Mater Sci Eng C Mater Biol Appl 29:2104–2109
Evanoff DD, Chumanov G (2005) Synthesis and optical properties of silver nanoparticles and arrays. Chemphyschem 6:1221–1231
Pillai ZS, Kamat PV (2004) What factors control the size and shape of silver nanoparticles in the citrate ion reduction method? J Phys Chem B 108:945–951
Pal A, Shah S, Kulkarni V, Murthy RSR, Devi S (2009) Template free synthesis of silver-gold alloy nanoparticles and cellular uptake of gold nanoparticles in Chinese Hamster Ovary cell. Mater Chem Phys 113:276–282
Hayat MA (1989) Colloidal gold: principles, methods, and applications. Academic, San Diego
Chumanov G, Sokolov K, Cotton TM (1996) Unusual extinction spectra of nanometer-sized silver particles arranged in two-dimensional arrays. J Phys Chem 100:5166–5168
Tullman JA, Finney WF, Lin YJ, Bishnoi SW (2007) Tunable assembly of peptide-coated gold nanoparticles. Plasmonics 2:119–127
Mallin MP, Murphy CJ (2002) Solution-phase synthesis of sub-10 nm Au–Ag alloy nanoparticles. Nano Lett 2:1235–1237
Yang Y, Gong X, Zeng H, Zhang L, Zhang X, Zou C, Huang S (2010) Combination of digestive ripening and seeding growth as a generalized route for precisely controlling size of monodispersed noble monometallic, shell thickness of core - shell and composition of alloy nanoparticles. The Journal of Physical Chemistry C 114:256–264
Gonzalez CM, Liu Y, Scaiano JC (2009) Photochemical strategies for the facile synthesis of gold–silver alloy and core-shell bimetallic nanoparticles. The Journal of Physical Chemistry C 113:11861–11867
Link S, Wang ZL, El-Sayed MA (1999) Alloy formation of gold-silver nanoparticles and the dependence of the plasmon absorption on their composition. J Phys Chem B 103:3529–3533
Chen HM, Liu RS, Jang LY, Lee JF, Hu SF (2006) Characterization of core-shell type and alloy Ag/Au bimetallic clusters by using extended X-ray absorption fine structure spectroscopy. Chem Phys Lett 421:118–123
Srnova-Sloufova I, Lednicky F, Gemperle A, Gemperlova J (2000) Core-shell (Ag)Au bimetallic nanoparticles: analysis of transmission electron microscopy images. Langmuir 16:9928–9935
Martins J, Oliva Teles L, Vasconcelos V (2007) Assays with Daphnia magna and Danio rerio as alert systems in aquatic toxicology. Environ Int 33:414–425
Wood C M, La Point T W, Armstrong D E, Birge W J, Brauner C J, Brix K V, Call D J, Crecelius E A, Davies P H, Gorsuch J W, Hogstrand C, Mahony J D, McGeer J C and O’Connor T P 2002 Silver in the environment: transport, fate, and effects, ed Andren A W and Bober T W (Pensacola, Florida: SETAC) pp 25–63
Acknowledgments
Financial funding for this work was provided through start-up funds provided to S.W.B. by the College of Science and Letters at the Illinois Institute of Technology. T.L. was funded through the Educational and Research Initiative Fund by the IIT Graduate College. M.R. and S.K. were funded through a Project SEED grant given by the American Chemical Society. L.I. was funded by an ACS Fellows grant given by the American Chemical Society. Additional support for materials and supplies were funded through the Physical Science Initiative Cohort Project by the Illinois State Board of Education. The authors thank Dr. Alan Nicholls, Interim Associate Director of the University of Illinois at Chicago’s Research Resource Center, for assistance with TEM collection. The authors also thank Kangmin Xu and Professor Xiaoping Qian for assistance with AFM measurements. The authors also thank Y. Huang, Y.J. Lin, D. Jezek, Professor Mitch Dushay, and Y. Cai for helpful discussions.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Li, T., Albee, B., Alemayehu, M. et al. Comparative toxicity study of Ag, Au, and Ag–Au bimetallic nanoparticles on Daphnia magna . Anal Bioanal Chem 398, 689–700 (2010). https://doi.org/10.1007/s00216-010-3915-1
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-010-3915-1