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Growth kinetics and long-term stability of CdS nanoparticles in aqueous solution under ambient conditions

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Abstract

The ubiquity of naturally occurring nanoparticles in the aquatic environment is now widely accepted, but a better understanding of the conditions that promote their formation and persistence is needed. Using cadmium sulfide (CdS) as a model metal sulfide species, thiolate-capped CdS nanoparticles were prepared in the laboratory to evaluate how aquatic conditions influence metal sulfide nanoparticle growth and stability. This work examines CdS nanoparticle growth directly in aqueous solution at room temperature by utilizing the size-dependent spectroscopic properties of semiconductors detectable by UV/vis. CdS nanoparticle growth was governed by oriented attachment, a non-classical mechanism of crystallization in which small precursor nanoparticles coalesce to form larger nanoparticle products. Nanoparticle growth was slowed with increasing capping agent and decreasing ionic strength. In addition to examining the short-term (hours) growth of the nanoparticles, a long-term study was conducted in which cysteine-capped CdS nanoparticles were monitored over 3 weeks in solutions of various ionic strengths. The long-term study revealed an apparent shift from small nanoparticles to nanoparticles twice their original size, suggesting nanoparticle growth may continue through oriented attachment over longer time scales. High-ionic strength solutions resulted in salt-induced aggregation and eventual settling of nanoparticles within days, whereas low-ionic strength solutions were stable against settling over the course of the experiment. Sulfide recovery from cysteine-capped CdS nanoparticles as acid volatile sulfide was nearly quantitative after 2 weeks in fully oxygenated water, demonstrating significantly slowed oxidation of sulfide when complexed to Cd(II) within CdS nanoparticles. The nanoparticles were also shown to be resistant to oxidation by Fe(III) (hydr)oxide. This study illustrates that aggregation, rather than chemical oxidation, is likely more important to the lifetime of many metal sulfide nanoparticles in the aquatic environment.

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References

  • Afonso MD, Stumm W (1992) Reductive dissolution of iron(III) (hydr)oxides by hydrogen sulfide. Langmuir 8:1671–1675

    Article  Google Scholar 

  • Ankley GT (1996) Evaluation of metal/acid-volatile sulfide relationships in the prediction of metal bioaccumulation by benthic macroinvertebrates. Environ Toxicol Chem 15:2138–2146

    Article  CAS  Google Scholar 

  • Baalousha M (2009) Aggregation and disaggregation of iron oxide nanoparticles: influence of particle concentration, pH and natural organic matter. Sci Total Environ 407:2093–2101

    Article  CAS  Google Scholar 

  • Bowles KC, Ernste MJ, Kramer JR (2003) Trace sulfide determination in oxic freshwaters. Anal Chim Acta 477:113–124

    Article  CAS  Google Scholar 

  • Brus LE (1984) Electron–electron and electron–hole interactions in small semiconductor crystallites—the size dependence of the lowest excited electronic state. J Chem Phys 80:4403–4409

    Article  CAS  Google Scholar 

  • Brus L (1986) Electronic wave-functions in semiconductor clusters—experiment and theory. J Phys Chem 90:2555–2560

    Article  CAS  Google Scholar 

  • Burleson DJ, Driessen MD, Penn RL (2004) On the characterization of environmental nanoparticles. J Environ Eng Health A 39:2707–2753

    Article  Google Scholar 

  • Cutter GA, Krahforst CF (1988) Sulfide in surface waters of the western Atlantic Ocean. Geophys Res Lett 15:1393–1396

    Article  CAS  Google Scholar 

  • De Jonge M, Dreesen F, De Paepe J, Blust R, Bervoets L (2009) Do acid volatile sulfides (AVS) influence the accumulation of sediment-bound metals to benthic invertebrates under natural field conditions? Environ Sci Technol 43:4510–4516

    Article  Google Scholar 

  • Deonarine A, Hsu-Kim H (2009) Precipitation of mercuric sulfide nanoparticles in nom-containing water: implications for the natural environment. Environ Sci Technol 43:2368–2373

    Article  CAS  Google Scholar 

  • Gammons CH, Frandsen AK (2001) Fate and transport of metals in H2S-rich waters at a treatment plant. Geochem Trans 2:1–15

    Article  Google Scholar 

  • Gilbert B, Banfield JF (2005) Molecular-scale processes involving nanoparticulate minerals in biogeochemical systems. Mol Geomicrobiol 59:109–155

    CAS  Google Scholar 

  • He YT, Wan JM, Tokunaga T (2008) Kinetic stability of hematite nanoparticles: the effect of particle sizes. J Nanopart Res 10:321–332

    Article  CAS  Google Scholar 

  • Henneke E, Luther GW, Delange GJ (1991) Determination of inorganic sulfur speciation with polarographic techniques—some preliminary results for recent hypersaline anoxic sediments. Mar Geol 100:115–123

    Article  CAS  Google Scholar 

  • Hochella MF, Lower SK, Maurice PA, Penn RL, Sahai N, Sparks DL, Twining BS (2008) Nanominerals, mineral nanoparticles, and Earth systems. Science 319:1631–1635

    Article  CAS  Google Scholar 

  • Hsu-Kim H, Mullaugh KM, Tsang JJ, Yucel M, Luther GW (2008) Formation of Zn- and Fe-sulfides near hydrothermal vents at the Eastern Lau Spreading Center: implications for sulfide bioavailability to chemoautotrophs. Geochem Trans 9

  • Huang F, Zhang HZ, Banfield JF (2003) Two-stage crystal-growth kinetics observed during hydrothermal coarsening of nanocrystalline ZnS. Nano Lett 3:373–378

    Article  CAS  Google Scholar 

  • Hyung H, Fortner JD, Hughes JB, Kim JH (2007) Natural organic matter stabilizes carbon nanotubes in the aqueous phase. Environ Sci Technol 41:179–184

    Article  CAS  Google Scholar 

  • Lau BLT, Hsu-Kim H (2008) Precipitation and growth of zinc sulfide nanoparticles in the presence of thiol-containing natural organic ligands. Environ Sci Technol 42:7236–7241

    Article  CAS  Google Scholar 

  • Luther GW, Rickard DT (2005) Metal sulfide cluster complexes and their biogeochemical importance in the environment. J Nanopart Res 7:389–407

    Article  CAS  Google Scholar 

  • Luther GW, Tsamakis E (1989) Concentration and form of dissolved sulfide in the oxic water column of the ocean. Mar Chem 27:165–177

    Article  CAS  Google Scholar 

  • Millero FJ, Hubinger S, Fernandez M, Garnett S (1987) Oxidation of H2S in seawater as a function of temperature, pH, and ionic strength. Environ Sci Technol 21:439–443

    Article  CAS  Google Scholar 

  • Moreau JW, Webb RI, Banfield JF (2004) Ultrastructure, aggregation-state, and crystal growth of biogenic nanocrystalline sphalerite and wurtzite. Am Miner 89:950–960

    CAS  Google Scholar 

  • Moreau JW, Weber PK, Martin MC, Gilbert B, Hutcheon ID, Banfield JF (2007) Extracellular proteins limit the dispersal of biogenic nanoparticles. Science 316:1600–1603

    Article  CAS  Google Scholar 

  • Morrison ID, Ross S (2002) Colloidal dispersions: suspensions, emulsions and foams. John Wiley and Sons, Inc, New York

    Google Scholar 

  • Mullaugh KM, Luther GW (2010) Spectroscopic determination of the size of cadmium sulfide nanoparticles formed under environmentally relevant conditions. J Environ Monit 12:890–897

    Article  CAS  Google Scholar 

  • Nowack B, Bucheli TD (2007) Occurrence, behavior and effects of nanoparticles in the environment. Environ Pollut 150:5–22

    Article  CAS  Google Scholar 

  • Penn RL (2004) Kinetics of oriented aggregation. J Phys Chem B 108:12707–12712

    Article  CAS  Google Scholar 

  • Poulton SW (2003) Sulfide oxidation and iron dissolution kinetics during the reaction of dissolved sulfide with ferrihydrite. Chem Geol 202:79–94

    Article  CAS  Google Scholar 

  • Poulton SW, Krom MD, Raiswell R (2004) A revised scheme for the reactivity of iron (oxyhydr)oxide minerals towards dissolved sulfide. Geochim Cosmochim Acta 68:3703–3715

    Article  CAS  Google Scholar 

  • Pyzik AJ, Sommer SE (1981) Sedimentary iron monosulfides: kinetics and mechanism of formation. Geochim Cosmochim Acta 45:687–698

    Article  CAS  Google Scholar 

  • Radford-Knëry J, Cutter GA (1994) Biogeochemistry of dissolved hydrogen sulfide species and carbonyl sulfide in the western North Atlantic Ocean. Geochim Cosmochim Acta 58:5421–5431

    Article  Google Scholar 

  • Rozan TF, Benoit G (1999) Geochemical factors controlling free Cu ion concentrations in river water. Geochim Cosmochim Acta 63:3311–3319

    Article  CAS  Google Scholar 

  • Rozan TF, Lassman ME, Ridge DP, Luther GW (2000) Evidence for iron, copper and zinc complexation as multinuclear sulphide clusters in oxic rivers. Nature 406:879–882

    Article  CAS  Google Scholar 

  • Stumm W (1992) Chemistry of the solid–water interface: processes at the mineral–water and particle–water interface in natural systems. John Wiley & Sons, New York

    Google Scholar 

  • Sukola K, Wang FY, Tessier A (2005) Metal sulfide species in oxic waters. Anal Chim Acta 528:183–195

    Article  CAS  Google Scholar 

  • Sundby B, Martinez P, Gobeil C (2004) Comparative geochemistry of cadmium, rhenium, uranium, and molybdenum in continental margin sediments. Geochim Cosmochim Acta 68:2485–2493

    Article  CAS  Google Scholar 

  • Theberge SM, Luther GW, Farrenkopf AM (1997) On the existence of free and metal complexed sulfide in the Arabian Sea and its oxygen minimum zone. Deep-Sea Res II 44:1381–1390

    Article  CAS  Google Scholar 

  • Tiemann M, Marlow F, Hartikainen J, Weiss O, Linden M (2008) Ripening effects in ZnS nanoparticle growth. J Phys Chem C 112:1463–1467

    Article  CAS  Google Scholar 

  • Vazquez F, Zhang JZ, Millero FJ (1989) Effects of metals on the rate of oxidation of H2S in seawater. Geophys Res Lett 16:1363–1366

    Article  Google Scholar 

  • Wigginton NS, Haus KL, Hochella MF (2007) Aquatic environmental nanoparticles. J Environ Monit 9:1306–1316

    Article  CAS  Google Scholar 

  • Yao WS, Millero FJ (1996) Oxidation of hydrogen sulfide by hydrous Fe(III) oxides in seawater. Mar Chem 52:1–16

    Article  CAS  Google Scholar 

  • Yücel M, Konovalov SK, Moore TS, Janzen CP, Luther GW (2010) Sulfur speciation in the upper Black Sea sediments. Chem Geol 269:364–375

    Article  Google Scholar 

  • Zhang ZH, Chin WS, Vittal JJ (2004) Water-soluble CdS quantum dots prepared from a refluxing single precursor in aqueous solution. J Phys Chem B 108:18569–18574

    Article  CAS  Google Scholar 

  • Zhang J, Lin Z, Lan YZ, Ren GQ, Chen DG, Huang F, Hong MC (2006) A multistep oriented attachment kinetics: coarsening of ZnS nanoparticle in concentrated NaOH. J Am Chem Soc 128:12981–12987

    Article  CAS  Google Scholar 

  • Zhang J, Wang YH, Zheng JS, Huang F, Chen DG, Lan YZ, Ren GQ, Lin Z, Wang C (2007) Oriented attachment kinetics for ligand capped nanocrystals: coarsening of thiol-PbS nanoparticles. J Phys Chem B 111:1449–1454

    Article  CAS  Google Scholar 

  • Zhang H, Liu Y, Zhang JH, Wang CL, Li MJ, Yang B (2008) Influence of interparticle electrostatic repulsion in the initial stage of aqueous semiconductor nanocrystal growth. J Phys Chem C 112:1885–1889

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors acknowledge Debbie Powell and Kirk Czymmek (Delware Biotechnology Institute) for help with TEM sample preparation and image analysis and Rovshan Mahmudov (UD Civil and Environmental Engineering) for help with DLS measurements. The authors would like to thank Dominic DiToro (UD Civil and Environmental Engineering) for thoughtful discussions that lead us to oriented attachment as a growth mechanism. This work was supported by the National Science Foundation under Grant No. EPS-0447610 (Delaware EPSCoR Seed Grant). Additional support was provided by a subcontract to the University of Delaware from the NASA Astrobiology grant to UC, Berkeley.

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Authors and Affiliations

  1. University of North Carolina Wilmington, Wilmington, NC, 28403, USA

    Katherine M. Mullaugh

  2. Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, 19716, USA

    Katherine M. Mullaugh & George W. Luther III

  3. College of Earth, Ocean and Environment, University of Delaware, Lewes, DE, 19958, USA

    George W. Luther III

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  1. Katherine M. Mullaugh
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  2. George W. Luther III
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Correspondence to Katherine M. Mullaugh.

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Mullaugh, K.M., Luther, G.W. Growth kinetics and long-term stability of CdS nanoparticles in aqueous solution under ambient conditions. J Nanopart Res 13, 393–404 (2011). https://doi.org/10.1007/s11051-010-0045-9

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