Metal-containing nanoparticles derived from concealed metal deposits: An important source of toxic nanoparticles in aquatic environments
Graphical abstract
Introduction
With the rapid development of nanoscience in the past decade, the applications of nano-materials in multiple industries have rapidly expanded (Banerjee et al., 2017; Cai et al., 2017; Dey et al., 2017; Gao et al., 2017; Parvanian et al., 2017; Priecel et al., 2016; Priyadarshini et al., 2016; Terzi et al., 2017; Wang et al., 2017). Subsequently, doubts concerning nanoparticle safety arose. Since 2003, top journals, such as Nature and Science, have published several articles indicating the potential negative effects of nanoparticles (Colvin, 2004; Nel et al., 2006; Schäfer, 2003; Service, 2008). After that, a number of studies demonstrated the adverse effects of nanoparticles to organisms, environment and ecosystems, especially concentrated on engineered nanoparticles, like SiO2 nanoparticles (Gambardella et al., 2015), TiO2 nanoparticles (Coccini et al., 2015) and iron oxide nanoparticles (Sadeghi et al., 2015). Besides, the toxicities of nanoparticles comprising heavy metals were especially prominent. For example, Bacchetta et al. (2017) showed that after 21-day exposures to ZnO nanoparticles and ZnSO4 nanoparticles at low concentrations (0.3 mg/L), Daphnia magna showed mitochondrial swelling, increased autophagy vacuole numbers, and significantly inhibited reproduction. Zhao et al. (2017) found that CuO nanoparticles induced significant growth inhibition on Eichhornia crassipes, whose root caps and meristematic zone were severely damaged after exposure. Zamani et al. (2014) also observed the negative effect of PbS nanoparticles on aquatic algae. Furthermore, nanoparticles containing heavy metals may be more toxic than common engineered nanoparticles containing light metals. For examples, Zijno et al. (2015) found that ZnO nanoparticles can result in genotoxicity, inducing micronuclei and DNA damage in cells, whereas TiO2 nanoparticles did not. Cells exposed to ZnO nanoparticles were not able to repair oxidative DNA damage but efficiently repaired after TiO2 exposure. All of these studies effectively confirmed the risk of nanoparticles, especially these nanoparticles comprising heavy metals, like Pb, Zn and Cu.
Contrast to the extensive attention on the environmental risks of engineered nanoparticles, naturally produced nanoparticles attracted attention only recently. Though several studies addressed some different naturally-occurring nanoparticles (Sharma et al., 2015; Wimmer et al., 2018), the environment risks of metal-bearing nanoparticles related to metal deposits, however, have never been mentioned. In fact, previous researches about ore exploration have mentioned this kind of nanoparticles associated with natural metal deposits (Cao et al., 2015; Hu et al., 2015; Li et al., 2016; Wang et al., 2016), but never considered about their environmental influences. Given the original toxicity of their heavy metal composition, metal-containing nanoparticles associated with natural metal deposits, were regarded to have played important but underappreciated roles.
On the other hand, the ecological risks of excessive metal element concentration around metal deposits have always been the research hotspot. Numerous studies have detailedly investigated the concentration of ore-related elements in various media, such as surface water (Liu et al., 2010), surface sediments (Meng et al., 2015), atmosphere (Castillo et al., 2013), arable soils and associated food crops (Obiora et al., 2016), herbaceous species (Stefanowicz et al., 2016). Almost without exception, the pollution and risks of metal deposits were always evaluated through the excessive concentrations of metal elements but did not consider metal-containing nanoparticles. However, some previous studies have suggested that metal-containing nanoparticles may pose greater risks to organisms than metal elements at relatively lower concentrations, because the toxicity of metal-bearing nanoparticles not only originated from their chemical composition but also their nanoparticle form. For example, Yin et al. (2011) suggested that growth inhibition and cell damage can be directly attributed to the nanoparticles themselves. Wirth et al. (2012) indicated a nanoparticle-specific toxicity in biofilm viability loss. Rodhe et al. (2015) and Moschini et al. (2013) respectively showed the higher danger of Cu nanoparticles and CuO nanoparticles than that of dissolved coppers. Gil-Allué’s study (2015) on stream periphyton further demonstrated that a specific Ag nanoparticles inhibition effect on one of the extracellular enzyme (leucine aminopeptidase) was independent of dissolved Ag. These studies forced us to pay more attention on the contaminant of metal deposits that occurred in the form of nanoparticles.
Since aquatic environment has always been an important study subject in the environment-associated studies (Furtado et al., 2015; Wheatland et al., 2017; Ayotte et al., 2017), risk study of naturally produced ore-related nanoparticles contained in aquatic environment seems especially important. Thus, Inner Mongolia, a province of gathered polymetallic deposits in China, was chosen as the study area, and water (including deep groundwater and residential well water) was chosen as the study object. High resolution TEM was used to analyze the potential occurrence of nanoparticles in these water samples. This study aimed to elucidate the existence of naturally produced ore-related nanoparticles in the aquatic environment and their potential risks, to fill the void of environmental studies about naturally produced ore-related nanoparticles, further provided help for establish corresponding risk assessment and monitoring systems.
Section snippets
Materials and methods
Water samples, including well water and deep groundwater samples were collected from 4 metal deposits in the Inner Mongolia autonomous region of China. The Shijiangshan, Chaihulanzi, Weilasituo and Dongshengmiao deposits were all investigated in this study. These chosen deposits have similar ore-forming elements. High grades of elements Pb and Zn occurred in all four deposits, other elements such as Cu, As, Cr, Sb also appeared in part deposits as the major ore-forming elements or associated
Results
As shown by TEM, numerous nanoparticles were found in both deep groundwater samples and well water samples from all four deposits, while the majority of these nanoparticles were metal-containing nanoparticles. The ore-forming elements of metal deposits significantly contributed to the chemical compositions of the nanoparticles found in corresponding water samples. Thereinto, Fe, Pb, Zn, Cu-containing nanoparticles were the most common types and As, Cr, Sn, Bi, Mn, Sb-containing nanoparticles
Original source, formation and migration of these metal-containing nanoparticles
The TEM study demonstrated the existence of naturally produced metal-containing nanoparticles in both deep groundwater samples and well water samples. Deep groundwater samples were directly collected from the deep mining adit, thus not surprising to be influenced by their corresponding ore-bodies. Based on the TEM-EDX analysis, high levels of similarities between the primary elemental compositions of the deep groundwater nanoparticles and the primary ore-forming elements of the corresponding
Declaration of interest form
Declarations of interest: none.
Acknowledgments
Financial support from the National Natural Science Foundation of China (Grant Nos. 41030425, 41473040 and 40773037). The authors wish to acknowledge Lin Zixia of the Instrument Analysis Center of the Yangzhou University for the assistance in microscopic analysis.
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