Differences in soil solution chemistry between soils amended with nanosized CuO or Cu reference materials: implications for nanotoxicity tests.

Soil toxicity tests for metal oxide nanoparticles often include micrometer-sized oxide and metal salt treatments to distinguish between toxicity from nanometer-sized particles, non-nanometer-sized particles, and dissolved ions. Test result will be confounded if each chemical form has different effects on soil solution chemistry. We report on changes in soil solution chemistry over 56 days-the duration of some standard soil toxicity tests-in three soils amended with 500 mg/kg Cu as nanometer-sized CuO (nano), micrometer-sized CuO (micrometer), or Cu(NO3)2 (salt). In the CuO-amended soils, the log Cu2+ activity was initially low (minimum -9.48) and increased with time (maximum -5.20), whereas in the salt-amended soils it was initially high (maximum -4.80) and decreased with time (minimum -6.10). The Cu2+ activity in the nano-amended soils was higher than in the micrometer-amended soils for at least the first 11 days, and lower than in the salt-amended soils for at least 28 d. The pH, and dissolved Ca and Mg concentrations in the CuO-amended soils were similar, but the salt-amended soils had lower pH for at least 14 d, and higher Ca and Mg concentrations throughout the test. Soil pretreatments such as leaching and aging prior to toxicity tests are suggested.

[1]  E. Valsami-Jones,et al.  Behavioural and biochemical responses of two marine invertebrates Scrobicularia plana and Hediste diversicolor to copper oxide nanoparticles. , 2011, Chemosphere.

[2]  D. Banerjee,et al.  Speciation of Metals in Sewage Sludge and Sludge-amended Soils , 2004 .

[3]  P. Paquin,et al.  Biotic ligand model of the acute toxicity of metals. 1. Technical Basis , 2001, Environmental toxicology and chemistry.

[4]  J. Whalen,et al.  Reproductive and behavioral responses of earthworms exposed to nano‐sized titanium dioxide in soil , 2012, Environmental toxicology and chemistry.

[5]  S. Sauvé,et al.  Copper Solubility and Speciation of In Situ Contaminated Soils: Effects of Copper Level, pH and Organic Matter , 1997 .

[6]  E. Lombi,et al.  Short‐term natural attenuation of copper in soils: Effects of time, temperature, and soil characteristics , 2006, Environmental toxicology and chemistry.

[7]  J. White,et al.  Xylem- and phloem-based transport of CuO nanoparticles in maize (Zea mays L.). , 2012, Environmental science & technology.

[8]  Jason M Unrine,et al.  Effects of particle size on chemical speciation and bioavailability of copper to earthworms (Eisenia fetida) exposed to copper nanoparticles. , 2010, Journal of environmental quality.

[9]  W. Silk,et al.  To duckweeds (Landoltia punctata), nanoparticulate copper oxide is more inhibitory than the soluble copper in the bulk solution. , 2011, Environmental pollution.

[10]  G. Lowry,et al.  Towards a definition of inorganic nanoparticles from an environmental, health and safety perspective. , 2009, Nature nanotechnology.

[11]  H. Kettles,et al.  Is soil acidification the cause of biochemical responses when soils are amended with heavy metal salts , 1999 .

[12]  Jun Chen,et al.  Relationship between solubility and solubility product: The roles of crystal sizes and crystallographic directions , 2006 .

[13]  Wenchao Du,et al.  TiO2 and ZnO nanoparticles negatively affect wheat growth and soil enzyme activities in agricultural soil. , 2011, Journal of environmental monitoring : JEM.

[14]  C. Chow,et al.  Copper toxicity, oxidative stress, and antioxidant nutrients. , 2003, Toxicology.

[15]  T. Ramachandran,et al.  A study of the antimicrobial property of encapsulated copper oxide nanoparticles on cotton fabric , 2011 .

[16]  E. Ruiz-Agudo,et al.  The mineral-water interface: Where minerals react with the environment , 2013 .

[17]  Jason M. Unrine,et al.  Biotic and abiotic interactions in aquatic microcosms determine fate and toxicity of Ag nanoparticles. Part 1. Aggregation and dissolution. , 2012, Environmental science & technology.

[18]  Stephen Lofts,et al.  Metal‐based nanoparticles in soil: Fate, behavior, and effects on soil invertebrates , 2012, Environmental toxicology and chemistry.

[19]  Karluss Thomas,et al.  Research strategies for safety evaluation of nanomaterials, part V: role of dissolution in biological fate and effects of nanoscale particles. , 2006, Toxicological sciences : an official journal of the Society of Toxicology.

[20]  J. Steevens,et al.  Assessing the fate and effects of nano aluminum oxide in the terrestrial earthworm, Eisenia fetida , 2010, Environmental toxicology and chemistry.

[21]  Y. Awakura,et al.  Acid dissolution of cupric oxide , 1980 .

[22]  N. Cedergreen,et al.  Soil pH effects on the comparative toxicity of dissolved zinc, non-nano and nano ZnO to the earthworm Eisenia fetida , 2014, Nanotoxicology.

[23]  Davey L. Jones,et al.  Comparative Toxicity of Nanoparticulate CuO and ZnO to Soil Bacterial Communities , 2012, PloS one.

[24]  I. Yruela Copper in plants: acquisition, transport and interactions. , 2009, Functional plant biology : FPB.

[25]  C. P. Rooney,et al.  A terrestrial biotic ligand model. 1. Development and application to Cu and Ni toxicities to barley root elongation in soils. , 2006, Environmental science & technology.

[26]  S. Sauvé,et al.  Ion-selective electrode measurements of copper(II) activity in contaminated soils , 1995 .

[27]  Dong-mei Zhou,et al.  Quantifying the adsorption and uptake of CuO nanoparticles by wheat root based on chemical extractions. , 2011, Journal of environmental sciences.

[28]  P. Paquin,et al.  Biotic ligand model of the acute toxicity of metals. 2. Application to acute copper toxicity in freshwater fish and Daphnia , 2001, Environmental toxicology and chemistry.

[29]  E. Smolders,et al.  Soil properties affecting the toxicity of CuCl2 and NiCl2 for soil microbial processes in freshly spiked soils , 2006, Environmental toxicology and chemistry.

[30]  William H. Hendershot,et al.  Spike/Leach Procedure to Prepare Soil Samples for Trace Metal Ecotoxicity Testing: Method Development Using Copper , 2013 .

[31]  L. Lavkulich,et al.  The Use of Zero Point of Charge (ZPC) to Assess Pedogenic Development 1 , 1978 .

[32]  D. Atha,et al.  Copper oxide nanoparticle mediated DNA damage in terrestrial plant models. , 2012, Environmental science & technology.

[33]  Lizhong Zhu,et al.  Toxicity of ZnO nanoparticles to Escherichia coli: mechanism and the influence of medium components. , 2011, Environmental science & technology.

[34]  D. Oughton,et al.  Aging and soil organic matter content affect the fate of silver nanoparticles in soil. , 2012, The Science of the total environment.

[35]  Anne Kahru,et al.  The Effect of Composition of Different Ecotoxicological Test Media on Free and Bioavailable Copper from CuSO4 and CuO Nanoparticles: Comparative Evidence from a Cu-Selective Electrode and a Cu-Biosensor , 2011, Sensors.

[36]  D. Chittleborough,et al.  Retention and dissolution of engineered silver nanoparticles in natural soils , 2012 .

[37]  A. Kahru,et al.  Toxicity of ZnO, TiO2 and CuO nanoparticles to microalgae Pseudokirchneriella subcapitata , 2008 .

[38]  R. Lanno,et al.  Determining exposure dose in soil: the effect of modifying factors on chlorinated benzene toxicity to earthworms. , 2009, Chemosphere.

[39]  C. A. V. van Gestel,et al.  Chronic toxicity of ZnO nanoparticles, non-nano ZnO and ZnCl2 to Folsomia candida (Collembola) in relation to bioavailability in soil. , 2011, Environmental pollution.

[40]  Christofer Leygraf,et al.  Surface characteristics, copper release, and toxicity of nano- and micrometer-sized copper and copper(II) oxide particles: a cross-disciplinary study. , 2009, Small.

[41]  Colin R. Janssen,et al.  Toxicity of Trace Metals in Soil as Affected by Soil Type and Aging After Contamination: Using Calibrated Bioavailability Models to Set Ecological Soil Standards , 2009, Environmental toxicology and chemistry.

[42]  Qasim Chaudhry,et al.  Considerations for environmental fate and ecotoxicity testing to support environmental risk assessments for engineered nanoparticles. , 2009, Journal of chromatography. A.

[43]  E. Lombi,et al.  The availability of copper in soils historically amended with sewage sludge, manure, and compost. , 2012, Journal of environmental quality.

[44]  Julien Rachou,et al.  Use of an ion-selective electrode for free copper measurements in low salinity and low ionic strength matrices , 2007 .

[45]  K. Kasemets,et al.  Toxicity of nanoparticles of CuO, ZnO and TiO2 to microalgae Pseudokirchneriella subcapitata. , 2009, The Science of the total environment.

[46]  A. Anderson,et al.  Responses of a soil bacterium, Pseudomonas chlororaphis O6 to commercial metal oxide nanoparticles compared with responses to metal ions. , 2011, Environmental pollution.