Influence of differently functionalized polystyrene microplastics on the toxic effects of P25 TiO2 NPs towards marine algae Chlorella sp.

Increased utilization of titanium dioxide nanoparticles (TiO2 NPs) for commercial as well as industrial purposes resulted in the accumulation of nanoparticles in the marine system. Microplastics being an emerging secondary pollutant in the marine ecosystem have an impact on the toxic effects of TiO2 NPs which has not been evaluated up to date. So it is important to assess the toxic effects of both these pollutants on the marine environment. The present study examines the impact of differently functionalized microplastics on the toxic effects of P25 TiO2 NPs to marine algae Chlorella sp. The tendency of nanoparticles to undergo aggregation in artificial seawater was observed with increase in time. The median effective concentration for TiO2 NPs was found to be 81 µM which indicates higher toxic effects of NPs toward algae. In contrast, microplastics irrespective of their difference in functionalization had minimal toxic effect of about 15% at their higher concentration tested, 1000 mg L-1. Plain and aminated polystyrene microplastics enhanced the TiO2 NPs toxicity which was further validated with oxidative stress determination studies like reactive oxygen species and lipid peroxidation assays. Negatively charged carboxylated polystyrene microplastics decreased the TiO2 NPs toxicity with possible hetero-aggregation between TiO2 NPs and microplastics in the system. The toxicity data obtained for the mixture was further corroborated with Abbott's mathematical model.

Dietary transfer of zinc oxide particles from algae (Scenedesmus obliquus) to daphnia (Ceriodaphnia dubia).

The rapid increase in production and usage of ZnO particles in recent years has instigated the concerns regarding their plausible effects on the environment. Current study explores the trophic transfer potential of ZnO particles of different sizes (50, 100 nm and bulk particles) from algae (Scenedesmus obliquus) to daphnia (Ceriodaphnia dubia) and the contribution of ZnO(ions) (effect of dissolved Zn ions that remain in test medium after separation NPs) to the overall toxicity of ZnO(total) (impact of both particle and dissolved Zn ions). Toxicity and uptake of ZnO(total) and ZnO(ions) in algae were found to be dependent on the concentration and particle size. Feeding of Zn accumulated algae (517 ±â€¯28, 354.7 ±â€¯61 and 291 ±â€¯20 µg/g dry wt.) post-exposure to 61 µM of ZnO(total) of 50, 100 nm and bulk ZnO particles caused a significant decrease in the survival (15-20%) of daphnia. A significant amount of Zn accumulation was observed in daphnia even after the 48 h depuration period. Biomagnification factor was found to be nearly 1 for all the sizes of ZnO particles tested. For 50 nm ZnO, the BMF was higher when compared to other two sizes, reaching the mean value of 1.06 ±â€¯0.01 at 61 µM. Further analysis revealed that the dietary uptake of different sizes of ZnO particles caused ultra-structural damages and degradation of internal organs in daphnia.

Trophic transfer potential of two different crystalline phases of TiO2 NPs from Chlorella sp. to Ceriodaphnia dubia.

Owing to the increase in the usage of titanium dioxide nanoparticles (TiO2 NPs), their release into the aquatic environment is inevitable. In the aquatic ecosystem, TiO2 NPs can bio-magnify at various trophic levels in the food chain through dietary exposure. In the current study, the trophic transfer potential of two crystalline phases of TiO2, anatase and rutile nanoparticles (individual as well as a binary mixture) has been evaluated in the lake water matrix using algae-daphnia system. Chlorella sp. and Ceriodaphnia dubia were used as test organisms to represent the algae-daphnia food chain of the freshwater ecosystem. Other than crystallinity, the effect of irradiation (visible and UV-A) was also investigated at the test concentrations, 75, 300, and 1200 µM. TiO2 NPs treated algal diet produced significant mortality only at the test concentrations, 300 and 1200 µM. The type of irradiation and crystallinity doesn't have any impact on the mortality of daphnids through the dietary exposure of TiO2 NPs. Comparing the mixture with individual NPs, binary mixture induced less mortality on C. dubia which signifies the antagonistic effect of NPs when they coexist. Statistical modeling confirmed the antagonistic effect of the binary mixture on C. dubia. As individual NPs, anatase and rutile forms showed a maximum Ti accumulation under UV-A and visible irradiation, respectively. BMF of TiO2 NPs has been in validation with the bioaccumulation noted in C. dubia. Individual NPs (75 µM) showed higher BMF value of ∼23 under both UV-A (anatase) and visible (rutile) irradiation. Individual NPs showing higher BMF confirmed their trophic transfer potential in the aquatic food chain, primarily through the diet. In contrast, the binary mixture obtained a higher BMF of 1.9 and 0.79 at 75 and 300 µM under visible and UV-A irradiation, respectively. The plausible reason behind this decrement was the antagonistic effect of the mixture which significantly reduced their Ti bioaccumulation on C. dubia.

Impact of tetracycline on the toxic effects of titanium dioxide (TiO2) nanoparticles towards the freshwater algal species, Scenedesmus obliquus.

Titanium dioxide nanoparticles (TiO2 NPs) are the most risk assessed nanoparticles in the aquatic environment due to their increased usage in the various sectors from electronics to consumer products. The natural aquatic system also comprises of numerous toxicants like antibiotics, whose impact on the toxicity of nanoparticles are less assessed. Hence, it is essential to determine the effect of other toxicants on the TiO2 NP toxicity. In the current study, the impact of antibiotic (tetracycline, TC) on the toxic effect of TiO2 NPs was studied on a freshwater alga, Scenedesmus obliquus. The median effective concentrations (EC50) of TiO2 NPs and TC were noted to be 136.88±2.30µM and 0.63±0.02µM, respectively. Based on the EC50 obtained, three different concentrations of TC, such as 0.34, 0.68, and 1.36µM have been selected to evaluate their effect on the toxicity of 18.75, 37.5, and 75µM of TiO2 NPs. Existence of TC provoked the growth inhibition of TiO2 NPs at their lower concentrations. In contrast, a reduction in the growth inhibition was noted as the concentrations of TC and TiO2 NPs were increased. Abbott modeling confirmed the additive and antagonistic effects noted. The stability profile of TiO2 NPs elucidated the aggregation of NPs with an increase in time. Even though a similar trend has been followed for TiO2 NPs+TC, a significant difference in the aggregation has not been observed in most cases when compared with TiO2 NPs alone. The presence of TC lowered the Ti uptake by the algal cells, which portrayed the dominance of TC in the toxic effect of TiO2 NPs to be either additive or antagonistic. The SEM images of the algal cells upon exposure to TiO2 NPs, TC, and their mixture elucidated the aggregation of algal cells, cellular deformations like compromised cell membrane, and vacuole formation, etc. In addition, the release of algal exudates was also noticed as a protective layer over the cells to counteract the stress. EPS secretion in response to TiO2 NPs along with TC is found to be in corroboration with the toxicity patterns observed.

Modulatory effects of Zn2+ ions on the toxicity of citrate- and PVP-capped gold nanoparticles towards freshwater algae, Scenedesmus obliquus.

Gold nanoparticles (GNPs) are widely used for medical purposes, both in diagnostics as well as drug delivery, and hence are prone to release and distribution in the environment. Thus, we have explored the effects of GNPs with two distinct surface capping (citrate and PVP), and three different sizes (16, 27, and 37 nm) at 0.01-, 0.1-, and 1-mg L-1 concentrations on a predominant freshwater alga Scenedesmus obliquus in the sterile freshwater matrix. We have also investigated how an abundant metal ion from freshwater, i.e., Zn2+ ions may modulate the effects of the selected GNPs (40 nm, citrate, and PVP capped). Preliminary toxicity results revealed that gold nanoparticles were highly toxic in comparison to zinc ions alone. A significant modulation in the toxicity of Zn ions was not noticed in the presence of GNPs. In contrast, zinc ions minimized the toxicity produced by GNPs (both CIT-37 and PVP-37), despite its individual toxicity. Approximately, about 42, 33, and 25% toxicity reduction was noted at 0.05-, 0.5-, and 5-mg L-1 Zn ions, respectively, for CIT-37 GNPs, while 31% (0.05 mg L-1), 24% (0.5 mg L-1), and 9% (5 mg L-1) of toxicity reduction were noted for PVP-37 GNPs. Maximum toxicity reduction was seen at 0.05 mg L-1 of Zn ions. Abbott modeling substantiated antagonistic effects offered by Zn2+ ions on GNPs. Stability and sedimentation data revealed that the addition of zinc ions gradually induced the aggregation of NPs and in turn significantly reduced the toxicity of GNPs. Thus, the naturally existing ions like Zn2+ have an ability to modulate the toxicity of GNPs in a real-world environment scenario.

Individual and binary toxicity of anatase and rutile nanoparticles towards Ceriodaphnia dubia.

Increasing usage of engineered nanoparticles, especially Titanium dioxide (TiO2) in various commercial products has necessitated their toxicity evaluation and risk assessment, especially in the aquatic ecosystem. In the present study, a comprehensive toxicity assessment of anatase and rutile NPs (individual as well as a binary mixture) has been carried out in a freshwater matrix on Ceriodaphnia dubia under different irradiation conditions viz., visible and UV-A. Anatase and rutile NPs produced an LC50 of about 37.04 and 48mg/L, respectively, under visible irradiation. However, lesser LC50 values of about 22.56 (anatase) and 23.76 (rutile) mg/L were noted under UV-A irradiation. A toxic unit (TU) approach was followed to determine the concentrations of binary mixtures of anatase and rutile. The binary mixture resulted in an antagonistic and additive effect under visible and UV-A irradiation, respectively. Among the two different modeling approaches used in the study, Marking-Dawson model was noted to be a more appropriate model than Abbott model for the toxicity evaluation of binary mixtures. The agglomeration of NPs played a significant role in the induction of antagonistic and additive effects by the mixture based on the irradiation applied. TEM and zeta potential analysis confirmed the surface interactions between anatase and rutile NPs in the mixture. Maximum uptake was noticed at 0.25 total TU of the binary mixture under visible irradiation and 1 TU of anatase NPs for UV-A irradiation. Individual NPs showed highest uptake under UV-A than visible irradiation. In contrast, binary mixture showed a difference in the uptake pattern based on the type of irradiation exposed.

Acute toxicity and accumulation of ZnO NPs in Ceriodaphnia dubia: Relative contributions of dissolved ions and particles.

Although the ecotoxicological effects of various metal oxide nanoparticles on aquatic organisms are being actively studied, the contributions of particles and dissolved ions towards toxicity are still not well understood. The current study aims to assess the contribution of ZnO NP(particle) and ZnO NP(ion) to the overall toxicity and accumulation of ZnO NP(total) in Ceriodaphnia dubia. The aggregation and dissolution kinetics were studied for three different sizes (50nm, 100nm and bulk) of ZnO particles at 0.05, 0.12, 0.25 and 0.5mg/L concentrations in the sterile lake water medium at 6, 12, 24, and 48h intervals. The 48h LC50 of ZnO NP(total) was found to be 0.431, 0.605 and 0.701mg/L for 50, 100nm and bulk particles exposure. However, LC50 of Zn(ion) was found to be 1.048, 1.343 and 2.046mg/L for dissolved ions from different sizes (50nm, 100nm, and bulk) of ZnO particles. At LC50 concentration, the accumulation of 90-95% was noted for the NP(particles) across the sizes employed, while only about 4-5% contribution was from the NP(ion) to the overall accumulation NP(total). The relative contribution of ZnO NP(ion) to overall toxicity and accumulation was found to be lesser than that of ZnO NP(particles) across the sizes used in the study.

Surface capping and size-dependent toxicity of gold nanoparticles on different trophic levels.

In the present study, the toxicity of gold nanoparticles (Au NPs) was evaluated on various trophic organisms. Bacteria, algae, cell line, and mice were used as models representing different trophic levels. Two different sizes (CIT30 and CIT40) and surface-capped (CIT30-polyvinyl pyrrolidone (PVP)-capped) Au NPs were selected. CIT30 Au NP aggregated more rapidly than CIT40 Au NP, while an additional capping of PVP (CIT30-PVP capped Au NP) was found to enhance its stability in sterile lake water medium. Interestingly, all the forms of NPs evaluated were stable in the cell culture medium during the exposure period. Size- and dose-dependent cytotoxicities were observed in both bacteria and algae, with a strong dependence on reactive oxygen species (ROS) generation and lactate dehydrogenase (LDH) release. CIT30-PVP capped Au NP showed a significant decrease in toxicity compared to CIT30 Au NP in bacteria and algae. In the SiHa cell line, dose- and exposure-dependent decline in cell viability were noted for all three types of Au NPs. In mice, the induction of DNA damage was size and dose dependent, and surface functionalization with PVP reduced the toxic effects of CIT30 Au NP. The exposure to CIT30, CIT40, and CIT30-PVP capped Au NPs caused an alteration of the oxidative stress-related endpoints in mice hepatocytes. The toxic effects of the gold nanoparticles were found to vary in diverse test systems, accentuating the importance of size and surface functionalization at different trophic levels.

Cytotoxicity of ZnO NPs towards fresh water algae Scenedesmus obliquus at low exposure concentrations in UV-C, visible and dark conditions.

Continuous increase in the usage of ZnO nanoparticles in commercial products has exacerbated the risk of release of these particles into the aquatic environment with possible harmful effects on the biota. In the current study, cytotoxic effects of two types of ZnO nanoparticles, having different initial effective diameters in filtered and sterilized lake water medium [487.5±2.55 nm for ZnO-1 NPs and 616.2±38.5 nm for ZnO-2 NPs] were evaluated towards a dominant freshwater algal isolate Scenedesmus obliquus in UV-C, visible and dark conditions at three exposure concentrations: 0.25, 0.5 and 1 mg/L. The toxic effects were found to be strongly dependent on the initial hydrodynamic particle size in the medium, the exposure concentrations and the irradiation conditions. The loss in viability, LDH release and ROS generation were significantly enhanced in the case of the smaller sized ZnO-1 NPs than in the case of ZnO-2 NPs under comparable test conditions. The toxicity of both types of ZnO NPs was considerably elevated under UV-C irradiation in comparison to that in dark and visible light conditions, the effects being more enhanced in case of ZnO-1 NPs. The size dependent dissolution of the ZnO NPs in the test medium and possible toxicity due to the released Zn(2+) ions was also noted. The surface adsorption of the nanoparticles was substantiated by scanning electron microscopy. The internalization/uptake of the NPs by the algal cells was confirmed by fluorescence microscopy, transmission electron microscopy, and elemental analyses.

Combined toxicity of two crystalline phases (anatase and rutile) of Titania nanoparticles towards freshwater microalgae: Chlorella sp.

In view of the increasing usage of anatase and rutile crystalline phases of titania NPs in the consumer products, their entry into the aquatic environment may pose a serious risk to the ecosystem. In the present study, the possible toxic impact of anatase and rutile nanoparticles (individually and in binary mixture) was investigated using freshwater microalgae, Chlorella sp. at low exposure concentrations (0.25, 0.5 and 1mg/L) in freshwater medium under UV irradiation. Reduction of cell viability as well as a reduction in chlorophyll content were observed due to the presence of NPs. An antagonistic effect was noted at certain concentrations of binary mixture such as (0.25, 0.25), (0.25, 0.5), and (0.5, 0.5) mg/L, and an additive effect for the other combinations, (0.25, 1), (0.5, 0.25), (0.5, 1), (1, 0.25), (1, 0.5), and (1, 1) mg/L. The hydrodynamic size analyses in the test medium revealed that rutile NPs were more stable in lake water than the anatase and binary mixtures [at 6h, the sizes of anatase (1mg/L), rutile NPs (1mg/L), and binary mixture (1, 1mg/L) were 948.83±35.01nm, 555.74±19.93nm, and 1620.24±237.87nm, respectively]. The generation of oxidative stress was found to be strongly dependent on the crystallinity of the nanoparticles. The transmission electron microscopic images revealed damages in the nucleus and cell membrane of algal cells due to the interaction of anatase NPs, whereas rutile NPs were found to cause chloroplast and internal organelle damages. Mis-shaped chloroplasts, lack of nucleus, and starch-pyrenoid complex were noted in binary-treated cells. The findings from the current study may facilitate the environmental risk assessment of titania NPs in an aquatic ecosystem.

A comparative ecotoxicity analysis of α- and γ-phase aluminium oxide nanoparticles towards a freshwater bacterial isolate Bacillus licheniformis.

Crystalline structure of nanoparticles may influence their physicochemical behaviour as well as their toxicological impact on biota. The differences in orientation of the atoms result in the variations in chemical stability. Thus, toxicological impacts of different crystalline phases of aluminium oxide nanoparticles are expected to vary. The present study brings out a comparative toxicity analysis of γ-phase and α-phase aluminium oxide nanoparticles of comparable hydrodynamic size range towards a freshwater bacterial isolate Bacillus licheniformis at low exposure concentrations (5, 1, 0.5 and 0.05 µg/mL). Upon 2-h exposure, the α-aluminium oxide particles showed lower toxicity than the γ-phase aluminium oxide. The lower level of oxidative stress generation and cell membrane damage in case of the α-phase aluminium oxide nanoparticles substantiated the toxicity results. The involvement of protein, lipopolysaccharides in nanoparticle-cell surface interaction, was noted in both the cases. To conclude, the crystallinity of aluminium oxide nanoparticles played an important role in the interaction and the toxicity response.

Different modes of TiO2 uptake by Ceriodaphnia dubia: relevance to toxicity and bioaccumulation.

The extensive environmental exposure of engineered metal oxide nanoparticles (NPs) may result in their bioaccumulation in aquatic organisms leading to their biotransfer in a food chain through various routes in a freshwater ecosystem. The present study focuses on the possible modes of TiO2 NP trophic transfer to Ceriodaphnia dubia, in presence and/absence of its diet, Scenedesmus obliquus (primary producer). The acute exposure studies (48h) were designed to have daphnids exposed to (i) the free NPs, (ii) both the free and the algae-borne NPs; and (iii) only the algae-borne NPs in separate tests to understand the possible routes of NP transfer. The dietary uptake of TiO2 NPs (algae-borne) was found to be the primary route for NP biotransfer with ∼70% of total NP uptake. Interestingly, in a separate study it was noticed that the NPs coated with algal exudates were easily taken up by daphnids as compared to pristine NPs of same concentrations, leading to their higher bioaccumulation. A chronic toxicity study, where daphnids were exposed to both free and algae-borne NPs for 21 days was undertaken to comprehend the TiO2 NP effect on daphnia growth and reproduction upon chronic exposure and also the bioaccumulation potential. Both acute and chronic exposure studies suggested higher bioaccumulation of TiO2 in daphnids when the particles were less toxic to the diet (algae).

Toxic effect of Cr(VI) in presence of n-TiO2 and n-Al2O3 particles towards freshwater microalgae.

The reactivity and toxicity of the soluble toxicants in the presence of the engineered nanomaterials is not well explored. In this study, the probable effects of TiO2 and Al2O3 nanoparticles (n-TiO2, n-Al2O3) on the toxicity of Cr(VI) were assessed with the dominant freshwater algae, Scenedesmus obliquus, in a low range of exposure concentrations (0.05, 0.5 and 1µg/mL). In the presence of 0.05µg/mL n-TiO2, the toxicity of Cr(VI) decreased considerably, which was presumably due to the Cr(VI) adsorption on the nanoparticle surface leading to its aggregation and precipitation. The elevated n-TiO2 concentrations (0.5 and 1µg/mL) did not significantly influence Cr(VI) bio-availability, and a dose dependent toxicity of Cr(VI) was observed. On the other hand, n-Al2O3 did not have any significant effect on the Cr(VI) toxicity. The microscopic observations presented additional information on the morphological changes of the algal cells in the presence of the binary toxicants. The generation of reactive oxygen species (ROS) suggested contribution of oxidative stress on toxicity and LDH release confirmed membrane permeability of algal cells upon stress.