Jiaoqin Liu

Effect of different carbon nanotubes on cadmium toxicity to Daphnia magna: The role of catalyst impurities and adsorption capacity.

Experiments were conducted to investigate the effect of four different carbon nanotubes single- and multi-walled carbon nanotubes (SWCNTs and MWCNTs) and hydroxylated and carboxylated multi-walled carbon nanotubes (OH-MWCNTs and COOH-MWCNTs) on Cd toxicity to the aquatic organism Daphnia magna. The acute toxicity results indicated that all CNTs could enhance the toxicity of Cd to D. magna. Furthermore, the filtrate toxicity and adsorption tests showed that the toxicity-increasing effect of SWCNTs and MWCNTs in the overall system was mainly caused by catalysts impurities from the pristine CNTs, whereas the greater adsorption of Cd onto OH-MWCNTs (30.52 mg/g) and COOH-MWCNTs (24.93 mg/g) was the key factor contributing to the enhanced toxicity. This result raised a concern that the metal catalyst impurities, adsorption capacities, and accumulation of waterborne CNTs were responsible for the toxicity of Cd to aquatic organism.

Evaluation of single and joint toxicity of perfluorooctane sulfonate and zinc to Limnodrilus hoffmeisteri: Acute toxicity, bioaccumulation and oxidative stress

Perfluorooctane sulfonate (PFOS) and zinc have been detected in aquatic environment widely. In order to study the combined effects of PFOS and Zn, a series of experiments was conducted to explore the acute mortality, bioaccumulation and antioxidant status of Limnodrilus hoffmeisteri. The acute toxicity was evaluated by calculating 24h-EC50 values, and it was observed that 24h-EC50 values in single and joint treatments decreased with decreasing pH value or increasing exposure concentration. Toxic unit analysis suggested that the combined effects of the PFOS+Zn binary mixture were mostly simple addition, with 8 groups showing synergism and only one group showing antagonism. The analysis of internal Zn and PFOS concentration showed that the possible interaction between Zn and PFOS can affect the bioaccumulation of the two chemicals in L. hoffmeisteri. In addition, oxidative stress status was assessed by measuring oxidation-related biochemical parameters such as superoxide dismutase, glutathione peroxidase and malondialdehyde, and the integrated biomarker response index was estimated to rank the toxicity order. Exposures to Zn and PFOS were found to evoke some changes in the antioxidant defense system, and a strong self-adaptive ability was noticed for L. hoffmeisteri after 10 d exposure.

Experimental and theoretical insights into the photochemical decomposition of environmentally persistent perfluorocarboxylic acids

Decomposition of perfluorocarboxylic acids (PFCAs) is of great significance due to their global distribution, persistence and toxicity to organisms. In this study, the photodegradation of a series of PFCAs (∼C2C12) in water by a medium-pressure mercury lamp was experimentally and theoretically examined. We found that photolysis of PFCAs all follow pseudo-first-order kinetics with the rate constant (kapp) increasing with carbon chain lengths, except for trifluoroacetic acid (TFA) which cannot be degraded by the polychromatic irradiation. Product analysis showed that the PFCAs were mainly decomposed into shorter carbon chain length PFCAs in a stepwise manner, with the accumulation of TFA and fluoride ions as the end products. Moreover, a small amount of perfluoroolefins (CnF2n) was determined as gas-phase products. Wiberg bond order calculations confirmed the cleavage of the CC bond between carboxylic carbon and the adjacent carbon as the first reaction step, and density functional theory-based calculations revealed that kapp value is correlated with some molecular structural parameters. In the case of mixture irradiation, the evolution profiles of individual PFCAs were different from that in single-component systems, due to the dynamic balance between production and degradation. This work reveals the main molecular descriptors controlling the degradation rate of different PFCAs species, and improves the general understanding on the photodegradation mechanisms, which will provide useful information for future researches.

Antioxidant defenses and histological changes in Carassius auratus after combined exposure to zinc and three multi-walled carbon nanotubes.

With the increasing applications of carbon nanotubes (CNTs) worldwide, considerable concerns have been raised regarding their inevitable releases into natural waters and ecotoxicity. It was supposed that CNTs may interact with some existing pollutants like zinc in aquatic systems and exhibit different effects when compared with their single treatments. However, data on their possible combined toxicity on aquatic species are still lacking. Moreover, the interactions of Zn with different functionalized CNTs may be distinct and thereby lead to diverse results. It is like that functional groups play a vital role in illustrating the differences in toxicity among various CNTs. In this study, the single and joint effects of multi-walled carbon nanotubes (MWCNTs) and two MWCNTs functionalized with carboxylation (COOH-MWCNTs) or hydroxylation (OH-MWCNTs) in the absence or presence of zinc (Zn) on antioxidant status and histopathological changes in Carassius auratus were evaluated. Synergistic effect was tentatively proposed for joint-toxicity action, which was supported by apparently observed oxidative stress and histopathological changes in joint exposure groups. The integrated biomarker response index was calculated to rank the toxicity order, from which the conclusion of synergistic effect was strengthened. Regarding differences among various CNTs, our data showed that OH-MWCNTs and COOH-MWCNTs were more stressful to fish than raw MWCNTs. This finding sustained that functionalization is an important factor in nanotoxicity, which may serve as clues for future design and application of CNTs. Overall, these results provided some valuable toxicological data on the joint effects of CNTs and heavy metals on aquatic species, which can facilitate further understanding on the potential impacts of other coexisting pollutants in the culture of freshwater fish.

The laccase-like reactivity of manganese oxide nanomaterials for pollutant conversion: rate analysis and cyclic voltammetry

Nanostructured manganese oxides, e.g. MnO2, have shown laccase-like catalytic activities, and are thus promising for pollutant oxidation in wastewater treatment. We have systematically compared the laccase-like reactivity of manganese oxide nanomaterials of different crystallinity, including α-, β-, γ-, δ-, and ɛ-MnO2, and Mn3O4, with 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulfonate) (ABTS) and 17β-estradiol (E2) as the probing substrates. The reaction rate behaviors were examined with regard to substrate oxidation and oxygen reduction to evaluate the laccase-like catalysis of the materials, among which γ-MnO2 exhibits the best performance. Cyclic voltammetry (CV) was employed to assess the six MnOx nanomaterials, and the results correlate well with their laccase-like catalytic activities. The findings help understand the mechanisms of and the factors controlling the laccase-like reactivity of different manganese oxides nanomaterials, and provide a basis for future design and application of MnOx-based catalysts.

Hydroxyl Radical Based Photocatalytic Degradation of Halogenated Organic Contaminants and Paraffin on Silica Gel

Photochemical materials are of scientific and practical importance in the field of photocatalysis. In this study, the photochemistry of several organic contaminants, including decabromodiphenyl ether (BDE-209), halogenated phenols (C6 X5OH, X = F, Cl, Br) and paraffin, on silica gel (SG) surface was investigated under simulated solar irradiation conditions. Photolysis of these compounds at the solid/air interface proceeds with different rates yielding various hydroxylation products, and hydroxyl radical was determined as the major reactive species. According to density functional theory (DFT) calculations, the reaction of physically adsorbed water with reactive silanone sites (>Si═O) on silica was indispensable for the generation of •OH radical, where the required energy matches well with the irradiation energy of visible light. Then, the BDE-209 was selected as a representative compound to evaluate the photocatalytic performance of SG under different conditions. The SG material showed good stability in the photodegradation process, and was able to effectively eliminate BDE-209 under natural sunlight. These findings provide new insights into the potential application of SG as a solid surface photocatalyst for contaminants removal.

Understanding the ozonated degradation of sulfadimethoxine, exploration of reaction site, and classification of degradation products

Ozonation has been demonstrated to be an efficient method of water treatment. In this study, the degradation of 20 mg/L of sulfadimethoxine (SDM) in different water matrices during ozonation was investigated. At pH 7.0, 100% removal of SDM was achieved by ozonation within 10 min. The degradation of SDM was more pronounced at acidic pH than under ambient environmental conditions, and was also dependent on different water matrices. Both direct and indirect oxidation of SDM by ozone were observed, and it was also shown that both ozone molecules and hydroxyl radicals were involved in the SDM degradation process, whereas it was found that the saturated ring of SDM made it O3-recalcitrant. Seven transformation products (TPs) were identified during SDM ozonation, allowing three degradation pathways to be proposed. Additionally, the main reaction sites, including N (7) and C (2) on the aniline ring, and the __S__N__ bond, were confirmed both experimentally and theoretically. The toxicity evolution during the degradation process was investigated, and the results showed no toxic intermediate products obtained during ozonation.