To duckweeds (Landoltia punctata), nanoparticulate copper oxide is more inhibitory than the soluble copper in the bulk solution

Shi, Jiyan; Abid, Aamir D.; Kennedy, Ian M.; Hristova, Krassimira R.; Silk, Wendy Kuhn

doi:10.1016/j.envpol.2011.01.028

Cited by 183 publications

(113 citation statements)

References 24 publications

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“…Increased suspended CBNPs in the presence of EPS may result in additional toxicity to sensitive species (in addition to toxicity from ions). 7 Effective regulation of CBNPs may therefore require particle-specific toxicological information (e.g., Shi et al 7 ) in addition to widely used data for copper ions and salts. Overall, results suggest that the long-term fate of CBNPs is the sediment phase, where they will persist.…”

Section: Speciationmentioning

confidence: 99%

Influence of Extracellular Polymeric Substances on the Long-Term Fate, Dissolution, and Speciation of Copper-Based Nanoparticles

Adeleye

Conway

Pérez

et al. 2014

Environ. Sci. Technol.

209

217

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ABSTRACT:The influence of phytoplankton-derived soluble extracellular polymeric substances (EPS), pH, and ionic strength (IS) on the dissolution, speciation, and stability of nano-CuO, nano-Cu, and Kocide (a micron sized Cu(OH) 2 -based fungicide) was investigated over 90 days. EPS improved the stability of commercial copper-based nanoparticles (CBNPs) in most conditions, in addition to influencing their dissolution. The dissolution rate was pH 4 ≫ pH 7 > pH 11. The presence of EPS correlated with higher dissolved Cu at pH 7 and 11, and lower dissolved Cu at pH 4. More dissolution was observed at higher IS (NaCl) due to complexation with Cl − . Dissolution of nano-CuO at pH 7 increased from 0.93% after 90 days (without EPS) to 2.01% (with 5 mg-C EPS/L) at 10 mM IS. Nano-CuO dissolved even more (2.42%) when IS was increased to 100 mM NaCl (with EPS). The ratio of freeCu 2+ /total dissolved Cu decreased in the presence of EPS, or as pH and/or IS increased. On a Cu mass basis, Kocide had the highest dissolved and suspended Cu at pH 7. However, dissolution of nano-Cu resulted in a higher fraction of free Cu 2+ , which may make nano-Cu more toxic to pelagic organisms. ■ INTRODUCTIONGlobal production of copper-based nanoparticles (CBNPs) was estimated at ∼200 t/yr in 2010, and is increasing. 1 CBNPs have found use in cosmetics, pigments, paints and coatings, electronics, and pesticides. 2−4 These applications may lead to direct exposure of CBNPs to the environment due to normal use, product wear-and-tear, and/or end-of-life disposal. 1 Toxicity of CBNPs and composites to organisms has been demonstrated. 2,5−8 It is therefore important to understand the long-term fate and transformations of these materials in aquatic systems in order to predict exposure to at-risk organisms.Stability and dissolution of engineered nanoparticles (ENPs) depend on ionic strength (IS), pH, and natural organic material (NOM). 9−12 Rapid aggregation of nano-Cu was reported in freshwater by Griffitt et al. 5 The authors also found that less than 0.1% of the nano-Cu dissolved in 48 h in the freshwater media used (pH 8.2). 98% dissolution of nano-Cu was however reported at pH 6 in "uterine-fluid" after a week, 13 demonstrating the importance of pH and media composition on CBNPs' dissolution. Mudunkotuwa and co-workers 14 reported increased dissolution of aged and new CBNPs in the presence of organic acids. Similarly, Worthington et al. 15 showed that the chitosan improved stability and dissolution of nano-Cu. To our knowledge, no studies have previously investigated the effects of naturally occurring NOM such as extracellular polymeric substances (EPS) on the stability and dissolution of CBNPs. EPS are synthesized by microorganisms, which are abundant in natural aquatic systems. EPS are mainly composed of polysaccharides, proteins, nucleic acids, and other polymers; and their composition may vary spatially and temporally even within the same species. 16 EPS may interact with ENPs, thus affecting their fate and transformation. 17 Additional...

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Section: Speciationmentioning

confidence: 99%

Influence of Extracellular Polymeric Substances on the Long-Term Fate, Dissolution, and Speciation of Copper-Based Nanoparticles

Adeleye

Conway

Pérez

et al. 2014

Environ. Sci. Technol.

209

217

View full text Add to dashboard Cite

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“…3 Since Cu ions are well-known to be toxic to many organisms, 32−34 processes that lower the amount of free Cu ions in solution may reduce the overall hazard of these ENMs. However, Cu ENM toxicity has been attributed to both ionic 22,35 and nanospecific 19,21,23,24 toxic effects, so even in waters with high organic content Cu-based ENMs may still pose a threat to aquatic organisms.…”

Section: Methodsmentioning

confidence: 99%

“…Depending on their composition, organic surface coatings can stabilize 14,15 or destabilize 8 particles in suspension and through the same mechanisms alter interactions between organisms and ENMs. 16,17 Previous research has shown that copper-based ENMs are toxic to a wide range of organisms, including fungi, 18 aquatic 19 and terrestrial plants, 20 estuarine amphipods, 21 daphnids and protozoa, 22 marine worms and clams, 23 and mussels. 24 It is therefore necessary to develop our understanding of how these materials behave once released into the environment in order to predict at-risk populations and properly regulate their manufacture, use, and disposal.…”

Section: +mentioning

confidence: 99%

Aggregation, Dissolution, and Transformation of Copper Nanoparticles in Natural Waters

Conway

Adeleye

Gardea‐Torresdey

et al. 2015

Environ. Sci. Technol.

237

180

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Time-dependent aggregation, sedimentation, dissolution, and transformation of three copper-based engineered nanomaterials (ENMs) of varied properties were measured in eight natural and artificial waters. Nano-Cu and Cu(OH) 2 aggregated rapidly to >10 3 nm while the aggregate size of nano-CuO averaged between 250 and 400 nm. Aggregate size for both nano-Cu and nano-CuO showed a positive correlation with ionic strength with a few exceptions. Aggregate size did not correlate well with sedimentation rate, suggesting sedimentation was influenced by other factors. Controlling factors in sedimentation rates varied by particle: Cu(OH) 2 particles remained stable in all waters but groundwater, nano-Cu was generally unstable except in waters with high organic content, and nano-CuO was stabilized by the presence of phosphate, which reversed surface charge polarity at concentrations as low as 0.1 mg PO 4 3− L −1. Dissolution generally correlated with pH, although in saline waters, dissolved copper formed insoluble complexes. Nano-Cu was rapidly oxidized, resulting in dissolution immediately followed by the formation of precipitates. These results suggest factors including phosphate, carbonate, and ENM oxidation state may be key in determining Cu ENM behavior in natural waters.

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“…However, this classification of dissolved Cu lumps together dissolved ions, nanoparticles (generally defined as particles with at least one dimension between 1 and 100 nm) and some bulk particles (100e450 nm in size). For proper risk assessment, it is necessary to determine how much of these different fractions of Cu are leached from antifouling paints since their fate, bioavailability, and toxicity differ considerably (Bielmyer-Fraser et al, 2014;Shi et al, 2011;Siddiqui et al, 2015;Thit et al, 2013;Torres-Duarte et al, 2015).…”

Section: Introductionmentioning

confidence: 99%

Release and detection of nanosized copper from a commercial antifouling paint

et al. 2016

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a b s t r a c tOne major concern with the use of antifouling paints is the release of its biocides (mainly copper and zinc) into natural waters, where they may exhibit toxicity to non-target organisms. While many studies have quantified the release of biocides from antifouling paints, very little is known about the physicochemical state of released copper. For proper risk assessment of antifouling paints, characterization of copper released into water is necessary because the physicochemical state determines the metal's environmental fate and effects. In this study, we monitored release of different fractions of copper (dissolved, nano, and bulk) from a commercial copper-based antifouling paint. Release from painted wood and aluminum mini-bars that were submerged in natural waters was monitored for 180 days. Leachates contained both dissolved and particulate copper species. X-ray diffraction and X-ray photoelectron spectroscopy were used to determine the chemical phase of particles in the leachate. The amount of copper released was strongly dependent on water salinity, painted surface, and paint drying time. The presence of nanosized Cu 2 O particles was confirmed in paint and its leachate using singleparticle inductively coupled plasma-mass spectrometry and electron microscopy. Toxicity of paint leachate to a marine phytoplankton was also evaluated.

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To duckweeds (Landoltia punctata), nanoparticulate copper oxide is more inhibitory than the soluble copper in the bulk solution

Cited by 183 publications

References 24 publications

Influence of Extracellular Polymeric Substances on the Long-Term Fate, Dissolution, and Speciation of Copper-Based Nanoparticles

Influence of Extracellular Polymeric Substances on the Long-Term Fate, Dissolution, and Speciation of Copper-Based Nanoparticles

Aggregation, Dissolution, and Transformation of Copper Nanoparticles in Natural Waters

Release and detection of nanosized copper from a commercial antifouling paint

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