Stream dynamics and chemical transformations control the environmental fate of silver and zinc oxide nanoparticles in a watershed-scale model.

Mathematical models are needed to estimate environmental concentrations of engineered nanoparticles (NPs), which enter the environment upon the use and disposal of consumer goods and other products. We present a spatially resolved environmental fate model for the James River Basin, Virginia, that explores the influence of daily variation in streamflow, sediment transport, and stream loads from point and nonpoint sources on water column and sediment concentrations of zinc oxide (ZnO) and silver (Ag) NPs and their reaction byproducts over 20 simulation years. Spatial and temporal variability in sediment transport rates led to high NP transport such that less than 6% of NP-derived metals were retained in the river and sediments. Chemical transformations entirely eliminated ZnO NPs and doubled Zn mobility in the stream relative to Ag. Agricultural runoff accounted for 23% of total metal stream loads from NPs. Average NP-derived metal concentrations in the sediment varied spatially up to 9 orders of magnitude, highlighting the need for high-resolution models. Overall, our results suggest that "first generation" NP risk models have probably misrepresented NP fate in freshwater rivers due to low model resolutions and the simplification of NP chemistry and sediment transport.

[1]  S F Tyrrel,et al.  Overland flow transport of pathogens from agricultural land receiving faecal wastes , 2003, Journal of applied microbiology.

[2]  Christoph Ort,et al.  Fate and transformation of silver nanoparticles in urban wastewater systems. , 2013, Water research.

[3]  Konrad Hungerbühler,et al.  Addressing the complexity of water chemistry in environmental fate modeling for engineered nanoparticles. , 2015, The Science of the total environment.

[4]  C. Haynes,et al.  Toxicity of engineered nanoparticles in the environment. , 2013, Analytical chemistry.

[5]  Enzo Lombi,et al.  Fate of zinc oxide nanoparticles during anaerobic digestion of wastewater and post-treatment processing of sewage sludge. , 2012, Environmental science & technology.

[6]  Dik van de Meent,et al.  Multimedia Modeling of Engineered Nanoparticles with SimpleBox4nano: Model Definition and Evaluation , 2014, Environmental science & technology.

[7]  B. Nowack,et al.  Exposure modeling of engineered nanoparticles in the environment. , 2008, Environmental science & technology.

[8]  Hansruedi Siegrist,et al.  Behavior of metallic silver nanoparticles in a pilot wastewater treatment plant. , 2011, Environmental science & technology.

[9]  Yoram Cohen,et al.  Multimedia environmental distribution of engineered nanomaterials. , 2014, Environmental science & technology.

[10]  Gregory V Lowry,et al.  Sulfidation processes of PVP-coated silver nanoparticles in aqueous solution: impact on dissolution rate. , 2011, Environmental science & technology.

[11]  Elizabeth A. Casman,et al.  Modeling nanosilver transformations in freshwater sediments. , 2013, Environmental science & technology.

[12]  Javier I. Amalvy,et al.  ポリウレタン/PTFEナノ粒子のコンポジットとナノコンポジットの表面特性,熱特性,および機械的特性 | 文献情報 | J-GLOBAL 科学技術総合リンクセンター , 2014 .

[13]  Shen Yu,et al.  Anthropogenic land uses elevate metal levels in stream water in an urbanizing watershed. , 2014, The Science of the total environment.

[14]  K. Hungerbühler,et al.  Comprehensive probabilistic modelling of environmental emissions of engineered nanomaterials. , 2014, Environmental pollution.

[15]  Anna M. Wise,et al.  Sulfidation of silver nanoparticles decreases Escherichia coli growth inhibition. , 2012, Environmental science & technology.

[16]  G. Lowry,et al.  Environmental transformations of silver nanoparticles: impact on stability and toxicity. , 2012, Environmental science & technology.

[17]  R. Scholz,et al.  Modeled environmental concentrations of engineered nanomaterials (TiO(2), ZnO, Ag, CNT, Fullerenes) for different regions. , 2009, Environmental science & technology.

[18]  P. Paquin,et al.  Predicting sediment metal toxicity using a sediment biotic ligand model: methodology and initial application , 2005, Environmental toxicology and chemistry.

[19]  Mervin D. Palmer,et al.  Water Quality Modeling: A Guide to Effective Practice , 2001 .

[20]  E. Peltier,et al.  Metal speciation in anoxic sediments: when sulfides can be construed as oxides. , 2005, Environmental science & technology.

[21]  D. K. Borah,et al.  WATERSHED-SCALE HYDROLOGIC AND NONPOINT-SOURCE POLLUTION MODELS: REVIEW OF MATHEMATICAL BASES , 2003 .

[22]  Jeffrey G. Arnold,et al.  Model Evaluation Guidelines for Systematic Quantification of Accuracy in Watershed Simulations , 2007 .

[23]  K. Hungerbühler,et al.  Estimation of cumulative aquatic exposure and risk due to silver: contribution of nano-functionalized plastics and textiles. , 2008, The Science of the total environment.

[24]  R. Schwarzenbach,et al.  Environmental Organic Chemistry , 1993 .

[25]  Antonio Marcomini,et al.  Agglomeration and sedimentation of titanium dioxide nanoparticles (n-TiO2) in synthetic and real waters , 2013, Journal of Nanoparticle Research.

[26]  Andrew C. Johnson,et al.  Nano silver and nano zinc-oxide in surface waters – Exposure estimation for Europe at high spatial and temporal resolution , 2015, Environmental pollution.

[27]  Di Toro,et al.  Sediment flux modeling , 2001 .

[28]  Elizabeth A. Casman,et al.  Modeling nanomaterial fate in wastewater treatment: Monte Carlo simulation of silver nanoparticles (nano-Ag). , 2013, The Science of the total environment.

[29]  Olivia H. Devereux ESTIMATES OF COUNTY-LEVEL NITROGEN AND PHOSPHORUS DATA FOR USE IN MODELING POLLUTANT REDUCTION , 2009 .

[30]  Arturo A. Keller,et al.  Emerging patterns for engineered nanomaterials in the environment: a review of fate and toxicity studies , 2014, Journal of Nanoparticle Research.

[31]  D van de Meent,et al.  Heteroaggregation and sedimentation rates for nanomaterials in natural waters. , 2014, Water research.

[32]  Arturo A Keller,et al.  Clay particles destabilize engineered nanoparticles in aqueous environments. , 2012, Environmental science & technology.

[33]  J. Lead,et al.  Transformations of nanomaterials in the environment. , 2012, Environmental science & technology.

[34]  Dik van de Meent,et al.  Natural colloids are the dominant factor in the sedimentation of nanoparticles , 2012, Environmental toxicology and chemistry.

[35]  Benjamin P Colman,et al.  Long-term transformation and fate of manufactured ag nanoparticles in a simulated large scale freshwater emergent wetland. , 2012, Environmental science & technology.

[36]  Arturo A. Keller,et al.  Predicted Releases of Engineered Nanomaterials: From Global to Regional to Local , 2014 .

[37]  R W Scholz,et al.  Engineered nanomaterials in rivers--exposure scenarios for Switzerland at high spatial and temporal resolution. , 2011, Environmental pollution.

[38]  Arturo A. Keller,et al.  Global life cycle releases of engineered nanomaterials , 2013, Journal of Nanoparticle Research.

[39]  Mitchell J. Small,et al.  Integrated Environmental Modeling: Pollutant Transport, Fate, and Risk in the Environment , 2005 .

[40]  Thilini P. Rupasinghe,et al.  Dissolution of ZnO nanoparticles at circumneutral pH: a study of size effects in the presence and absence of citric acid. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[41]  A A Koelmans,et al.  Lake retention of manufactured nanoparticles. , 2015, Environmental pollution.

[42]  Albert A Koelmans,et al.  Rapid settling of nanoparticles due to heteroaggregation with suspended sediment , 2014, Environmental toxicology and chemistry.

[43]  M. A. Kiser,et al.  Nanomaterial Removal and Transformation During Biological Wastewater Treatment , 2013 .

[44]  J. Pizzuto Long‐term storage and transport length scale of fine sediment: Analysis of a mercury release into a river , 2014 .

[45]  Anthony J. Jakeman,et al.  A review of erosion and sediment transport models , 2003, Environ. Model. Softw..

[46]  Thilini P. Rupasinghe,et al.  Aggregation and dissolution of 4 nm ZnO nanoparticles in aqueous environments: influence of pH, ionic strength, size, and adsorption of humic acid. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[47]  Josep Galceran,et al.  Dissolution Kinetics and Solubility of ZnO Nanoparticles Followed by AGNES , 2012 .

[48]  Gordon E. Brown,et al.  Sulfidation mechanism for zinc oxide nanoparticles and the effect of sulfidation on their solubility. , 2013, Environmental science & technology.

[49]  Hong Zhang,et al.  Accumulation and risk of heavy metals in relation to agricultural intensification in the river sediments of agricultural regions , 2014, Environmental Earth Sciences.

[50]  Konrad Hungerbühler,et al.  Development of environmental fate models for engineered nanoparticles--a case study of TiO2 nanoparticles in the Rhine River. , 2012, Environmental science & technology.

[51]  Wei-Chun Chin,et al.  Zinc oxide–engineered nanoparticles: Dissolution and toxicity to marine phytoplankton , 2010, Environmental toxicology and chemistry.

[52]  Mark R Wiesner,et al.  Importance of heterogeneous aggregation for NP fate in natural and engineered systems. , 2014, The Science of the total environment.

[53]  T. C. Daniel,et al.  Managing Agricultural Phosphorus for Protection of Surface Waters: Issues and Options , 1994 .

[54]  O. T. Mefford,et al.  Physical transformations of iron oxide and silver nanoparticles from an intermediate scale field transport study , 2014, Journal of Nanoparticle Research.

[55]  Ventura River Reaches Environmental Protection Agency Environmental Protection Agency Environmental Protection Agency Environmental Protection Agency Environmental Protection Agency , 2012 .

[57]  E. Crecelius,et al.  Relationship between acid volatile sulfide and the toxicity of zinc, lead and copper in marine sediments , 1994 .

[58]  Martin Hassellöv,et al.  Geographically distributed classification of surface water chemical parameters influencing fate and behavior of nanoparticles and colloid facilitated contaminant transport. , 2013, Water research.

[59]  Lisa Truong,et al.  Sulfidation of silver nanoparticles: natural antidote to their toxicity. , 2013, Environmental science & technology.

[60]  Chikashi Sato,et al.  Processes, coefficients, and models for simulating toxic organics and heavy metals in surface waters , 1987 .

[61]  U. Förstner,et al.  Sediment Dynamics and Pollutant Mobility in Rivers , 2007 .

[62]  Enzo Lombi,et al.  X-ray absorption and micro X-ray fluorescence spectroscopy investigation of copper and zinc speciation in biosolids. , 2011, Environmental science & technology.

[63]  Björn A. Sandén,et al.  Challenges in Exposure Modeling of Nanoparticles in Aquatic Environments , 2011 .

[64]  G. E. Gadd,et al.  Comparative toxicity of nanoparticulate ZnO, bulk ZnO, and ZnCl2 to a freshwater microalga (Pseudokirchneriella subcapitata): the importance of particle solubility. , 2007, Environmental science & technology.

[65]  B. Jefferson,et al.  Fate of zinc oxide and silver nanoparticles in a pilot wastewater treatment plant and in processed biosolids. , 2014, Environmental science & technology.