Shibin Li

An evaluation of the impact of multiwalled carbon nanotubes on soil microbial community structure and functioning

This study evaluated the impacts of multiwalled carbon nanotubes (MWNTs) on microbial community composition and functioning in a sandy loam soil over 90 d. We used test concentrations in the range of lower MWNT concentrations (10mg/kg) to extremely high MWNT concentrations (10,000 mg/kg) as a worst case scenario. We observed no effects of MWNTs on soil respiration, enzymatic activities, and microbial community composition at 10, 100 and 1,000 mg/kg. However, increases in fungal fatty acid methyl ester markers were observed at the highest treatment. In addition, pyrosequencing demonstrated a decreased abundance of some bacterial genera like Derxia, Holophaga, Opitutus and Waddlia at the highest treatment while bacterial genera that are considered potential degraders of recalcitrant contaminants (such as polycyclic aromatic hydrocarbons) like Rhodococcus, Cellulomonas, Nocardioides and Pseudomonas increased. These results suggest a shift in soil microbial community composition to more tolerant microbial populations in the presence of extremely high MWNT concentrations. It is unlikely that the change observed at 10,000 mg/kg is due to metal or carbon impurities as the MWNTs used in this study were of high purity. Given the need for wide-ranging data for regulation and risk assessment of nanomaterials, this study provides valuable data.

Impact of solar UV radiation on toxicity of ZnO nanoparticles through photocatalytic reactive oxygen species (ROS) generation and photo-induced dissolution.

The present study investigated the impact of solar UV radiation on ZnO nanoparticle toxicity through photocatalytic ROS generation and photo-induced dissolution. Toxicity of ZnO nanoparticles to Daphnia magna was examined under laboratory light versus simulated solar UV radiation (SSR). Photocatalytic ROS generation and particle dissolution were measured on a time-course basis. Two toxicity mitigation assays using CaCl2 and N-acetylcysteine were performed to differentiate the relative importance of these two modes of action. Enhanced ZnO nanoparticle toxicity under SSR was in parallel with photocatalytic ROS generation and enhanced particle dissolution. Toxicity mitigation by CaCl2 to a less extent under SSR than under lab light demonstrates the role of ROS generation in ZnO toxicity. Toxicity mitigation by N-acetylcysteine under both irradiation conditions confirms the role of particle dissolution and ROS generation. These findings demonstrate the importance of considering environmental solar UV radiation when assessing ZnO nanoparticle toxicity and risk in aquatic systems.

Determination of multi-walled carbon nanotube bioaccumulation in earthworms measured by a microwave-based detection technique.

Reliable quantification techniques for carbon nanotubes (CNTs) are limited. In this study, a new procedure was developed for quantifying multi-walled carbon nanotubes (MWNTs) in earthworms (Eisenia fetida) based on freeze drying and microwave-induced heating. Specifically, earthworms were first processed into a powder by freeze drying. Then, samples were measured by utilizing 10 s exposure to 30 W microwave power. This method showed the potential to quantitatively measure MWNTs in earthworms at low concentrations (~0.1 μg in 20 mg of earthworm). Also, a simple MWNT bioaccumulation study in earthworms indicated a low bioaccumulation factor of 0.015±0.004. With an appropriate sample processing method and instrumental parameters (power and exposure time), this technique has the potential to quantify MWNTs in a variety of sample types (plants, earthworms, human blood, etc.).

Mobility of polyaromatic hydrocarbons (PAHs) in soil in the presence of carbon nanotubes

Being a potential risk to the environment, a fate study of carbon nanotube (CNT) in the environment is urgently needed. A study of CNT impacts on the bioavailability of other conventional contaminants in a terrestrial system is particularly rare. This study explored PAH leaching behaviors in the presence of CNTs with column leaching tests. Four PAHs (Naphthalene, fluorene, phenanthrene, and pyrene), three CNTs (f-SWNTs, MWNTs, f-MWNTs), and a sandy loam soil were involved in this study. We found that at a concentration of 5mg/g, CNTs could significantly retain PAHs in soil. Such a strong PAH retention was caused by low mobilities of CNTs and their strong PAH sorption capacities. This study illustrated that the properties of both sorbents (e.g. available surface area and micropore volume) and sorbates (e.g. hydrophobicity and molecular volume) influenced the mobility of PAHs in soil.

Comparative studies of multi-walled carbon nanotubes (MWNTs) and octadecyl (C18) as sorbents in passive sampling devices for biomimetic uptake of polycyclic aromatic hydrocarbons (PAHs) from soils

To avoid overestimating the risk of polycyclic aromatic hydrocarbons (PAHs), research is needed to evaluate the bioavailable portion of PAHs in the environment. However, limited PSDs were developed for a terrestrial soil system. In this study, two sorbents, octadecyl (C18) and multi-walled carbon nanotubes (MWNTs), were individually evaluated as sorbents in passive sampling devices (PSDs) as biomimetic samplers to assess the uptake of PAHs from soil. C18-PSDs were an excellent biomimetic tool for PAHs with a low molecular weight in complex exposure conditions with different soil types, types of PAHs, aging periods, and initial PAH concentrations in soil. The utility of MWNT-PSDs was limited by extraction efficiencies of PAHs from MWNTs. However, when compared to C18-PSDs, they had higher adsorption capacities and were less expensive. This study provides data regarding useful techniques that can be used in risk assessment to assess the bioavailability of PAHs in soil.

Chronic TiO2 nanoparticle exposure to a benthic organism, Hyalella azteca: impact of solar UV radiation and material surface coatings on toxicity

There is limited information on the chronic effects of nanomaterials to benthic organisms, as well as environmental mitigating factors that might influence this toxicity. The present study aimed to fill these data gaps by examining various growth endpoints (weight gain, instantaneous growth rate, and total protein content) for up to a 21 d sediment exposure of TiO2 nanoparticles (nano-TiO2) to a representative benthic species, Hyalella azteca. An uncoated standard, P25, and an Al(OH)3 coated nano-TiO2 used in commercial products were added to sediment at 20 mg/L or 100 mg/L Under test conditions, UV exposure alone was shown to be a greater cause of toxicity than even these high levels of nano-TiO2 exposure, indicating that different hazards need to be addressed in toxicity testing scenarios. In addition, this study showed the effectiveness of a surface coating on the decreased photoactivity of the material, as the addition of an Al(OH)3 coating showed a dramatic decrease in reactive oxygen species (ROS) production. However, this reduced photoactivity was found to be partially restored when the coating had been degraded, leading to the need for future toxicity tests which examine the implications of weathering events on particle surface coatings.

Impact of natural organic matter on particle behavior and phototoxicity of titanium dioxide nanoparticles

Due to their inherent phototoxicity and inevitable environmental release, titanium dioxide nanoparticles (nano-TiO2) are increasingly studied in the field of aquatic toxicology. One of the particular interests is the interactions between nano-TiO2 and natural organic matter (NOM). In this study, a series of experiments was conducted to study the impacts of Suwannee River natural organic matter (SRNOM) on phototoxicity and particle behaviors of nano-TiO2. For Daphnia magna, after the addition of 5mg/L SRNOM, LC50 value decreased significantly from 1.03 (0.89-1.20) mg/L to 0.26 (0.22-0.31) mg/L. For zebrafish larvae, phototoxic LC50 values were 39.9 (95% CI, 25.9-61.2) mg/L and 26.3 (95% CI, 18.3-37.8) mg/L, with or without the presence of 5mg/L SRNOM, respectively. There was no statistically significant change of these LC50 values. The impact of SRNOM on phototoxicity of nano-TiO2 was highly dependent on test species, with D. magna being the more sensitive species. The impact on particle behavior was both qualitatively and quantitatively examined. A global predictive model for particle behavior was developed with a three-way interaction of SRNOM, TiO2 concentration, and time and an additive effect of ionic strength. Based on power analyses, 96-h exposure in bioassays was recommended for nanoparticle-NOM interaction studies. The importance of reactive oxygen species (ROS) quenching of SRNOM was also systematically studied using a novel exposure system that isolates the effects of environmental factors. These experiments were conducted with minimal impacts of other important interaction mechanisms (NOM particle stabilization, NOM UV attenuation, and NOM photosensitization). This study highlighted both the particle stabilization and ROS quenching effects of NOM on nano-TiO2 in an aquatic system. There is an urgent need for representative test materials, together with key environmental factors, for future risk assessment and regulations of nanomaterials.

Modeling TiO2 nanoparticle phototoxicity: The importance of chemical concentration, ultraviolet radiation intensity, and time

As a semiconductor with wide band gap energy, TiO2 nanoparticles (nano-TiO2) are highly photoactive, and recent efforts have demonstrated phototoxicity of nano-TiO2 to aquatic organisms. However, a dosimetry model for the phototoxicity of nanomaterials that incorporates both direct UV and photo-activated chemical toxicity has not yet been developed. In this study, a set of Hyalella azteca acute toxicity bioassays at multiple light intensities and nano-TiO2 concentrations, and with multiple diel light cycles, was conducted to assess how existing phototoxicity models should be adapted to nano-TiO2. These efforts demonstrated (a) adherence to the Bunsen-Roscoe law for the reciprocity of light intensity and time, (b) no evidence of damage repair during dark periods, (c) a lack of proportionality of effects to environmental nano-TiO2 concentrations, and (d) a need to consider the joint effects of nano-TiO2 phototoxicity and direct UV toxicity.

An integrated approach for identifying priority contaminant in the Great Lakes Basin – Investigations in the Lower Green Bay/Fox River and Milwaukee Estuary areas of concern

Environmental assessment of complex mixtures typically requires integration of chemical and biological measurements. This study demonstrates the use of a combination of instrumental chemical analyses, effects-based monitoring, and bio-effects prediction approaches to help identify potential hazards and priority contaminants in two Great Lakes Areas of Concern (AOCs), the Lower Green Bay/Fox River located near Green Bay, WI, USA and the Milwaukee Estuary, located near Milwaukee, WI, USA. Fathead minnows were caged at four sites within each AOC (eight sites total). Following 4d of in situ exposure, tissues and biofluids were sampled and used for targeted biological effects analyses. Additionally, 4d composite water samples were collected concurrently at each caged fish site and analyzed for 132 analytes as well as evaluated for total estrogenic and androgenic activity using cell-based bioassays. Of the analytes examined, 75 were detected in composite samples from at least one site. Based on multiple analyses, one site in the East River and another site near a paper mill discharge in the Lower Green Bay/Fox River AOC, were prioritized due to their estrogenic and androgenic activity, respectively. The water samples from other sites generally did not exhibit significant estrogenic or androgenic activity, nor was there evidence for endocrine disruption in the fish exposed at these sites as indicated by the lack of alterations in ex vivo steroid production, circulating steroid concentrations, or vitellogenin mRNA expression in males. Induction of hepatic cyp1a mRNA expression was detected at several sites, suggesting the presence of chemicals that activate the aryl hydrocarbon receptor. To expand the scope beyond targeted investigation of endpoints selected a priori, several bio-effects prediction approaches were employed to identify other potentially disturbed biological pathways and related chemical constituents that may warrant future monitoring at these sites. For example, several chemicals such as diethylphthalate and naphthalene, and genes and related pathways, such as cholinergic receptor muscarinic 3 (CHRM3), estrogen receptor alpha1 (esr1), chemokine ligand 10 protein (CXCL10), tumor protein p53 (p53), and monoamine oxidase B (Maob), were identified as candidates for future assessments at these AOCs. Overall, this study demonstrates that a better prioritization of contaminants and associated hazards can be achieved through integrated evaluation of multiple lines of evidence. Such prioritization can guide more comprehensive follow-up risk assessment efforts.

An “EAR” on Environmental Surveillance and Monitoring: A Case Study on the Use of Exposure–Activity Ratios (EARs) to Prioritize Sites, Chemicals, and Bioactivities of Concern in Great Lakes Waters

Current environmental monitoring approaches focus primarily on chemical occurrence. However, based on concentration alone, it can be difficult to identify which compounds may be of toxicological concern and should be prioritized for further monitoring, in-depth testing, or management. This can be problematic because toxicological characterization is lacking for many emerging contaminants. New sources of high-throughput screening (HTS) data, such as the ToxCast database, which contains information for over 9000 compounds screened through up to 1100 bioassays, are now available. Integrated analysis of chemical occurrence data with HTS data offers new opportunities to prioritize chemicals, sites, or biological effects for further investigation based on concentrations detected in the environment linked to relative potencies in pathway-based bioassays. As a case study, chemical occurrence data from a 2012 study in the Great Lakes Basin along with the ToxCast effects database were used to calculate exposure-activity ratios (EARs) as a prioritization tool. Technical considerations of data processing and use of the ToxCast database are presented and discussed. EAR prioritization identified multiple sites, biological pathways, and chemicals that warrant further investigation. Prioritized bioactivities from the EAR analysis were linked to discrete adverse outcome pathways to identify potential adverse outcomes and biomarkers for use in subsequent monitoring efforts.