Jean-Claude J. Bonzongo

Effects of particle composition and species on toxicity of metallic nanomaterials in aquatic organisms

Metallic nanoparticles are among the most widely used types of engineered nanomaterials; however, little is known about their environmental fate and effects. To assess potential environmental effects of engineered nanometals, it is important to determine which species are sensitive to adverse effects of various nanomaterials. In the present study, zebrafish, daphnids, and an algal species were used as models of various trophic levels and feeding strategies. To understand whether observed effects are caused by dissolution, particles were characterized before testing, and particle concentration and dissolution were determined during exposures. Organisms were exposed to silver, copper, aluminum, nickel, and cobalt as both nanoparticles and soluble salts as well as to titanium dioxide nanoparticles. Our results indicate that nanosilver and nanocopper cause toxicity in all organisms tested, with 48-h median lethal concentrations as low as 40 and 60 microg/L, respectively, in Daphnia pulex adults, whereas titanium dioxide did not cause toxicity in any of the tests. Susceptibility to nanometal toxicity differed among species, with filter-feeding invertebrates being markedly more susceptible to nanometal exposure compared with larger organisms (i.e., zebrafish). The role of dissolution in observed toxicity also varied, being minor for silver and copper but, apparently, accounting for most of the toxicity with nickel. Nanoparticulate forms of metals were less toxic than soluble forms based on mass added, but other dose metrics should be developed to accurately assess concentration-response relationships for nanoparticle exposures.

Aluminum drinking water treatment residuals (Al-WTRs) as sorbent for mercury: implications for soil remediation.

The potential of readily available and non-hazardous waste material, aluminum drinking water treatment residuals (Al-WTRs), to efficiently sorb and immobilize mercury (Hg) from aqueous solutions was evaluated. Al-WTR samples with average specific surface area of 48m(2)/g and internal micropore surface area of 120m(2)/g were used in a series of batch sorption experiments. Obtained sorption isotherms indicated a strong affinity of Hg for Al-WTRs. Using the Langmuir adsorption model, a relatively high maximum sorption capacity of 79mg Hg/g Al-WTRs was determined. Sorption kinetic data was best fit to a pseudo-first-order model, while the use of the Weber-Morris and Bangham models suggested that the intraparticle diffusion could be the rate-limiting step. Also, Al-WTRs effectively immoblized Hg in the pH range of 3-8. The results from these short-term experiments demonstrate that Al-WTRs can be effectively used to remove Hg from aqueous solutions. This ability points to the potential of Al-WTRs as a sorbent in soil remediation techniques based on Hg-immobilization.

Increasing UV-B radiation at the earth's surface and potential effects on aqueous mercury cycling and toxicity.

In the past two decades, a great deal of attention has been paid to the environmental fate of mercury (Hg), and this is exemplified by the growing number of international conferences devoted uniquely to Hg cycling and its impacts on ecosystem functions and life. This interest in the biogeochemistry of Hg has resulted in a significant improvement of our understanding of its impact on the environment and human health. However, both past and current research, have been primarily oriented toward the study of direct impact of anthropogenic activities on Hg cycling. Besides a few indirect effects such as the increase in Hg methylation observed in acid-rain impacted aquatic systems or the reported enhanced Hg bioaccumulation in newly flooded water reservoirs; changes in Hg transformations/fluxes that may be related to global change have received little attention. A case in point is the depletion of stratospheric ozone and the resulting increase in solar UV-radiation reaching the Earth. This review and critical discussion suggest that increasing UV-B radiation at earths surface could have a significant and complex impact on Hg cycling including effects on Hg volatilization (photo-reduction), solubilization (photo-oxidation), methyl-Hg demethylation, and Hg methylation. Therefore, this paper is written to provoke discussions, and more importantly, to stimulate research on potential impacts of incoming solar UV-radiation on global Hg fluxes and any toxicity aspects of Hg that may become exacerbated by UV-radiation.

Heavy Metals in Sediments of the Gold Mining Impacted Pra River Basin, Ghana, West Africa

Total concentrations of Hg, Al, Fe, As, Pb, Cu, Cr, Ni, Mn, Co, V, and Zn were determined in surface sediments collected from 21 locations within the gold mining impacted Pra River basin in southwestern Ghana. Samples were collected during both the rainy and dry seasons. We hypothesized that in the rural southwestern portion of Ghana, the lack of industrial activities makes artisanal gold mining (AGM) by Hg amalgamation the main source of water resource contamination with heavy metals. Therefore, metals showing concentration trends similar to that of Hg in the studied system are likely impacted by AGM. We found that total-Hg (THg) concentrations in riverine sediments are rather low as compared to other aquatic systems that are impacted by similar mining activities. Measured THg concentrations ranged from 0.018 to 2.917 mg/kg in samples collected in the rainy season and from about 0.01 to 0.043 mg/kg in those collected during the dry season. However, the determination of the enrichment factor (EF) calculated using shale data as reference background values showed signs of severe contamination in most of the sampled sites. In the dry season, THg concentrations correlated positively and significantly to the concentrations of As (r = 0.864, p < 0.01), Cu (r = 0.691, p < 0.05), and Ni (r = 0.579, p < 0.05). Based on our previously stated hypothesis, this could then be an indication of the impact of AGM on ambient levels of these 3 elements. However, the determined concentrations of Cu, and Ni co-varied significantly with Al, suggesting that natural sources do account for the observed levels. Accordingly, both AGM and metal inputs from weathered natural deposits are likely co-responsible for the observed levels of Cu and Ni. In contrast, the lack of correlation between As and Al tends to suggest an impact of AGM on As levels. Overall, our data suggest that besides Hg and to some extent As, the impact of AGM on ambient levels of investigated metals in the gold mining impacted Pra River remains negligible. Finally, the increase in metal concentrations from the dry to the rainy season underlines the impact of changes in hydrologic conditions on levels and fate of metals in this tropical aquatic system.

Effects of natural water chemistry on nanosilver behavior and toxicity to Ceriodaphnia dubia and Pseudokirchneriella subcapitata

The success of nanotechnology will undoubtedly lead to the increased introduction of nanoparticles (NPs) into natural systems, and aquatic systems will likely act as sinks for these new pollutants. Differences in the chemistry of these aquatic systems will control changes in surface properties of NPs and therefore could impact their environmental fate and toxicity. A series of batch experiments was conducted to determine the effect of natural waters with different solution chemistries on nanosilver (nAg) particle dispersion, stability, and toxicity. Toxicity assays were performed in tested natural waters as well as in traditional growth media. Briefly, nAg suspended in a natural water with a low ionic strength/dissolved organic carbon (DOC) ratio had an average particle size of 76.8 ± 0.4 nm and was less toxic to Ceriodaphnia dubia and Pseudokirchneriella subcapitata (median lethal concentration [LC50] = 221 ppb and median inhibition concentration [IC50] = 1,600 ppb, respectively), whereas a natural water with a high ionic strength/DOC ratio had an average particle size of 192 ± 5.1 nm and produced a much higher toxicity response (LC50 = 0.433 ppb and IC50 = 22.6 ppb, respectively). These findings help to establish needed correlations between water-matrix-dependent nAg particle properties and toxicity implications and indicate that the use of traditional growth media in toxicity assays concerning engineered NPs might not always be appropriate.

Interactive Forces between Sodium Dodecyl Sulfate-Suspended Single-Walled Carbon Nanotubes and Agarose Gels

Selective adsorption onto agarose gels has become a powerful method to separate single-walled carbon nanotubes (SWCNTs). A better understanding of the nature of the interactive forces and specific sites responsible for adsorption should lead to significant improvements in the selectivity and yield of these separations. A combination of nonequilibrium and equilibrium studies are conducted to explore the potential role that van der Waals, ionic, hydrophobic, π-π, and ion-dipole interactions have on the selective adsorption between agarose and SWCNTs suspended with sodium dodecyl sulfate (SDS). The results demonstrate that any modification to the agarose gel surface and, consequently, the permanent dipole moments of agarose drastically reduces the retention of SWCNTs. Because these permanent dipoles are critical to retention and the fact that SDS-SWCNTs function as macro-ions, it is proposed that ion-dipole forces are the primary interaction responsible for adsorption. The selectivity of adsorption may be attributed to variations in polarizability between nanotube types, which create differences in both the structure and mobility of surfactant. These differences affect the enthalpy and entropy of adsorption, and both play an integral part in the selectivity of adsorption. The overall adsorption process shows a complex behavior that is not well represented by the Langmuir model; therefore, calorimetric data should be used to extract thermodynamic information.

Mitigation of the impact of single-walled carbon nanotubes on a freshwater green algae: Pseudokirchneriella subcapitata

Abstract This study investigates the biological response of Pseudokirchneriella subcapitata to single-walled carbon nanotubes (SWNTs) suspended in gum Arabic (GA), using typical 96-hour algal bioassays and long-term growth studies. Changes in algal biomass and cell morphology associated with specific SWNT-treatments were monitored and the mechanisms of observed biological responses investigated through a combination of biochemical and spectroscopic methods. Results from short-term bioassays showed a growth inhibition in culture media containing >0.5 mg SWNT/L and a final GA concentration of 0.023% (v/v). Interestingly, the observed toxicity disappears when GA concentrations are brought to levels ≥ 0.046%. Long-term experiments based on toxic combination of SWNTs and GA showed that P. subcapitata would easily recover from an initial growth inhibition effect. Overall, these findings point to the possibility of GA to mitigate the toxicity of SWNTs, making it an ideal surfactant if SWNT suspension in GA does not alter the performance sought from these nanotubes.

Nanowastes and the environment: Using mercury as an example pollutant to assess the environmental fate of chemicals adsorbed onto manufactured nanomaterials

Emerging nanotechnologies hold great promise for creating new means of detecting pollutants, cleaning polluted waste streams, and recovering materials before they become wastes, thereby protecting environmental quality. Studies focusing on the different advantages of nanoscience and nanotechnology abound in the literature, but less research effort seems to be directed toward studying the fate and potential impacts of wastes that will be generated by this technology. Using a combination of biogeochemical and toxicological methods, we conducted a preliminary investigation of the potential environmental fate of Hg as an example pollutant bound to nanomaterials used in treatment of gas effluents. Methylation of Hg sorbed onto SiO(2)-TiO(2) nanocomposites was used as a proxy for Hg bioavailability to sedimentary microorganisms, and the FluoroMetPLATE assay was used to assess the toxicity of both virgin and Hg-loaded SiO(2)-TiO(2) nanocomposites. Our results show that the bioavailability of Hg sorbed onto SiO(2)-TiO(2) nanocomposites to sedimentary microorganisms is pH dependent, with decreasing reaction rates as the pH increases from 4 to 6. Toxicity tests conducted using liquid extracts obtained by leaching of Hg-loaded SiO(2)-TiO(2) nanocomposites with the synthetic precipitation leaching procedure solution showed an average inhibition of 84% (vs 57% for virgin SiO(2)-TiO(2) nanocomposites). These results suggest that Hg sorbed onto engineered nanoparticles could become bioavailable and toxic if introduced into natural systems. Accordingly, studies focusing on the environmental implications of nanomaterials should include determination of the fate and impacts of pollutants that enter the environment bound to engineered nanomaterials.

Effects of engineered nanomaterials on microbial catalyzed biogeochemical processes in sediments

Engineered nanomaterials (ENMs) are anticipated to find use in many human activities and commercial products. Concerns are therefore being raised regarding their environmental fate and toxicological implications, which remain largely unknown. In this study, we investigate the effects of C(60), nano-Ag and CdSe quantum dots (QD) on microbial-catalyzed oxidation of organic matter in freshwater sediments. Sediment slurries spiked with sodium acetate at a final concentration of 150 mg/L were separately treated with pre-identified toxic levels of the tested ENMs. The study focused primarily on acetate oxidation by nitrate reducing bacteria. Sediment slurries were incubated under anaerobic conditions in parallel with control samples, and changes in concentrations of acetate, nitrate and nitrite tracked over time. The results showed that tested C(60) concentration completely inhibited the microbial oxidation of acetate, whereas the addition of nano-Ag and CdSe QD to sediment slurries negatively affected the rates of acetate oxidation. Under conditions with nitrate as prevalent electron acceptor, reaction rates of acetate degradation decreased from 0.44 day(-1) in control slurries to 0.24 day(-1) and 0.20 day(-1) in slurries treated with nano-Ag and CdSe QD, respectively. These preliminary results call for further investigations on potential long-term effects of ENMs on microbial driven basic ecosystem services.

Aqueous suspension methods of carbon-based nanomaterials and biological effects on model aquatic organisms.

The preparation of aqueous suspensions of carbon-based nanomaterials (NMs) requires the use of dispersing agents to overcome their hydrophobic character. Although studies on the toxicity of NMs have focused primarily on linking the characteristics of particles to biological responses, the role of dispersing agents has been overlooked. This study assessed the biological effects of a number of commonly used dispersing agents on Pseudokirchneriella subcapitata and Ceriodaphnia dubia as model test organisms. The results show that for a given organism, NM toxicity can be mitigated by use of nontoxic surfactants, and that a multispecies approach is necessary to account for the sensitivity of different organisms. In addition to the intrinsic physicochemical properties of NMs, exposure studies should take into account the effects of used dispersing fluids.