Aquatic Toxicity Effects and Risk Assessment of 'Form Specific' Product-Released Engineered Nanomaterials.

The study investigated the toxicity effects of 'form specific' engineered nanomaterials (ENMs) and ions released from nano-enabled products (NEPs), namely sunscreens, sanitisers, body creams and socks on Pseudokirchneriella subcapitata, Spirodela polyrhiza, and Daphnia magna. Additionally, risk estimation emanating from the exposures was undertaken. The ENMs and the ions released from the products both contributed to the effects to varying extents, with neither being a uniform principal toxicity agent across the exposures; however, the effects were either synergistic or antagonistic. D. magna and S. polyrhiza were the most sensitive and least sensitive test organisms, respectively. The most toxic effects were from ENMs and ions released from sanitisers and sunscreens, whereas body creams and sock counterparts caused negligible effects. The internalisation of the ENMs from the sunscreens could not be established; only adsorption on the biota was evident. It was established that ENMs and ions released from products pose no imminent risk to ecosystems; instead, small to significant adverse effects are expected in the worst-case exposure scenario. The study demonstrates that while ENMs from products may not be considered to pose an imminent risk, increasing nanotechnology commercialization may increase their environmental exposure and risk potential; therefore, priority exposure cases need to be examined.

Exposure Media and Nanoparticle Size Influence on the Fate, Bioaccumulation, and Toxicity of Silver Nanoparticles to Higher Plant Salvinia minima.

Silver nanoparticles (AgNPs) are favoured antibacterial agents in nano-enabled products and can be released into water resources where they potentially elicit adverse effects. Herein, interactions of 10 and 40 nm AgNPs (10-AgNPs and 40-AgNPs) with aquatic higher plant Salvinia minima at 600 µg/L in moderately hard water (MHW), MHW of raised calcium (Ca2+), and MHW containing natural organic matter (NOM) were examined. The exposure media variants altered the AgNPs' surface properties, causing size-dependent agglomeration. The bio-accessibility in the ascending order was: NOM < MHW < Ca2+, was higher in plants exposed to 10-AgNPs, and across all exposures, accumulation was higher in roots compared to fronds. The AgNPs reduced plant growth and the production of chlorophyll pigments a and b; the toxic effects were influenced by exposure media chemistry, and the smaller 10-AgNPs were commonly the most toxic relative to 40-AgNPs. The toxicity pattern was linked to the averagely higher dissolution of 10-AgNPs compared to the larger counterparts. The scanning electron microscopy and X-ray fluorescence analytical techniques were found limited in examining the interaction of the plants with AgNPs at the low exposure concentration used in this study, thus challenging their applicability considering the even lower predicted environmental concentrations AgNPs.

Characterisation of Engineered Nanomaterials in Nano-Enabled Products Exhibiting Priority Environmental Exposure.

Analytical limitations have constrained the determination of nanopollution character from real-world sources such as nano-enabled products (NEPs), thus hindering the development of environmental safety guidelines for engineered nanomaterials (ENMs). This study examined the properties of ENMs in 18 commercial products: sunscreens, personal care products, clothing, and paints-products exhibiting medium to a high potential for environmental nanopollution. It was found that 17 of the products contained ENMs; 9, 3, 3, and 2 were incorporated with nTiO2, nAg, binaries of nZnO + nTiO2, and nTiO2 + nAg, respectively. Commonly, the nTiO2 were elongated or angular, whereas nAg and nZnO were near-spherical and angular in morphology, respectively. The size ranges (width × length) were 7-48 × 14-200, 34-35 × 37-38, and 18-28 nm for nTiO2, nZnO, and nAg respectively. All ENMs were negatively charged. The total concentration of Ti, Zn, and Ag in the NEPs were 2.3 × 10-4-4.3%, 3.4-4.3%, and 1.0 × 10-4-11.3 × 10-3%, respectively. The study determined some key ENM characteristics required for environmental risk assessment; however, challenges persist regarding the accurate determination of the concentration in NEPs. Overall, the study confirmed NEPs as actual sources of nanopollution; hence, scenario-specific efforts are recommended to quantify their loads into water resources.

Fate and behavior of ZnO- and Ag-engineered nanoparticles and a bacterial viability assessment in a simulated wastewater treatment plant.

The fate and behaviour assessment of ZnO- and Ag-engineered nanoparticles (ENPs) and bacterial viability in a simulated wastewater treatment plant (WWTP) fed with municipal wastewater was investigated through determination of ENPs stability at varying pH and continuous exposure of ENPs to wastewater, respectively. The ENPs were introduced to a 3-L bioreactor (simulated WWTP) with a hydraulic residence time (HRT) of 6 h at a dose rate of 0.83 mg/min for 240 h. The stability of the ENPs was found to be dependent on their dissolution and aggregation at different pH, where ZnO ENPs exhibited the highest dissolution at low pH compared to Ag ENPs. The results also showed that both ENPs had high affinity for the sewage sludge as they undergo aggregation under typical wastewater conditions. Results of effluent monitored daily showed mean COD removal efficiencies of 71 ± 7% and 74 ± 8% for ZnO and Ag ENPs in test units, respectively. The treated effluent had low mean concentrations of Zn (1.39 ± 0.54 mg/L) and Ag (0.12 ± 0.06 mg/L); however, elevated mean concentrations of Zn (54 ± 39 mg/g dry sludge) and Ag (57 ± 42 mg/g dry sludge) were found in the sludge - suggesting removal of the ENPs from the wastewater by biosorption and biosolid settling mechanisms. Using X-ray diffraction (XRD) and transmission electron microscopy (TEM), the mineral identities of ZnO and Ag ENPs in the sludge from the test units were found comparable to those of commercial ENPs, but larger due to agglomeration. The bacterial viability assessment after exposure to ENPs using the Live/Dead BacLight kit, although not quantitatively assessed, suggested high resilience of the bacteria useful for biodegradation of organic material in the simulated wastewater treatment system.

Synthesis and Characterization of MC/TiO2 NPs Nanocomposite for Removal of Pb2+ and Reuse of Spent Adsorbent for Blood Fingerprint Detection.

The removal of toxic heavy metals from wastewater through the use of novel adsorbents is expensive. The challenge arises after the heavy metal is removed by the adsorbent, and the fate of the adsorbent is not taken care of. This may create secondary pollution. The study aimed to prepare mesoporous carbon (MC) from macadamia nutshells coated with titanium dioxide nanoparticles (TiO2 NPs) using a hydrothermal method to remove Pb2+ and to test the effectiveness of reusing the lead-loaded spent adsorbent (Pb2+-MC/TiO2 NP nanocomposite) in blood fingerprint detection. The samples were characterized using SEM, which confirmed spherical and flower-like structures of the nanomaterials, whereas TEM confirmed a particle size of 5 nm. The presence of functional groups such as C and Ti and a crystalline size of 4 nm were confirmed by FTIR and XRD, respectively. The surface area of 1283.822 m2/g for the MC/TiO2 NP nanocomposite was examined by BET. The removal of Pb2+ at pH 4 and the dosage of 1.6 g/L with the highest percentage removal of 98% were analyzed by ICP-OES. The Langmuir isotherm model best fit the experimental data, and the maximum adsorption capacity of the MC/TiO2 NP nanocomposite was 168.919 mg/g. The adsorption followed the pseudo-second-order kinetic model. The ΔH° (-54.783) represented the exothermic nature, and ΔG° (-0.133 to -4.743) indicated that the adsorption process is spontaneous. In the blood fingerprint detection, the fingerprint details were more visible after applying the Pb2+-MC/TiO2 NP nanocomposite than before the application. The reuse application experiments showed that the Pb2+-MC/TiO2 NP nanocomposite might be a useful alternative material for blood fingerprint enhancement when applied on nonporous surfaces, eliminating secondary pollution.

Improving capacity for phytoremediation of Vetiver grass and Indian mustard in heavy metal (Al and Mn) contaminated water through the application of clay minerals.

One of the consequences of mining is the release of heavy metals into the environment, especially water bodies. Phytoremediation of areas contaminated by heavy metals using Vetiver grass and Indian mustard is cost-effective and environmentally friendly. This study aimed at enhancing remediation of heavy metal contaminated water through the simultaneous hybrid application of clay minerals (attapulgite and bentonite) and Vetiver grass or Indian mustard. A 21-day greenhouse experiment was carried out to investigate the effectiveness of the clay minerals to improve heavy metal phytoremediation. The highest accumulation of aluminium (Al) by Vetiver grass was 371.8 mg/kg in the BT2.5VT treatment, while for Mn, the highest accumulation of 34.71 mg/kg was observed in the AT1VT treatment. However, Indian mustard showed no significant uptake of heavy metals, but suffered heavy metal toxicity despite the addition of clay minerals. From this study, it was evident that bentonite added at 2.5% (w/v) could improve the phytoremediation capacity of Vetiver grass for Al and Mn polluted water. The current laboratory-scale findings provided a basis for field trials earmarked for remediation in a post-mining coal environment in South Africa. This remediation approach can also be adopted in other places.

The antibacterial effects of engineered nanomaterials: implications for wastewater treatment plants.

Nanotechnology is currently at the forefront of scientific research and technological developments that have resulted in the manufacture of novel consumer products and numerous industrial applications using engineered nanomaterials (ENMs). With the increasing number of applications and uses of ENMs comes an increasing likelihood of nanoscale materials posing potential risks to the environment and engineered technical systems such as wastewater treatment plants (WWTPs). Recent scientific data suggests that ENMs that are useful in, for example, medical applications due to their novel physicochemical properties, may also cause adverse effects to the bacterial populations used in wastewater treatment systems. In this review, the toxicological effects of titanium nanoparticles (nTiO(2)), zinc oxide (nZnO), carbon nanotubes (CNTs), fullerenes (C(60)) and silver nanoparticles (AgNPs) to bacteria were examined. The results suggest that the potential ENMs risks to bacteria are non-uniform (need to be assessed case-by-case), and are dependent on numerous factors (e.g. size, pH, surface area, natural organic matter). Currently available data are therefore insufficient for evaluating the risks that ENMs pose in WWTPs. To fill these knowledge gaps, we recommend scenario specific studies aimed at improving our understanding on: (i) estimated volumes of ENMs in effluents, (ii) the antibacterial sensitivity of cultures within WWTPs towards selected ENMs, and (iii) processes improving the stability of ENMs in solutions. Two factors that merit consideration for elucidating the potential risks systematically are the toxicity mechanisms of ENMs to bacteria, and the influencing factors based on inherent physicochemical properties and environmental factors. Furthermore, the complexity of behaviour and fate of ENMs in real WWTPs requires case studies for assessing the ENMs risks to bacteria in vivo. The current laboratory results derived using simplified exposure media do not reflect actual environmental conditions.

Assessment of Nanopollution from Commercial Products in Water Environments.

The use of nano-enabled products (NEPs) can release engineered nanomaterials (ENMs) into water resources, and the increasing commercialisation of NEPs raises the environmental exposure potential. The current study investigated the release of ENMs and their characteristics from six commercial products (sunscreens, body creams, sanitiser, and socks) containing nTiO2, nAg, and nZnO. ENMs were released in aqueous media from all investigated NEPs and were associated with ions (Ag+ and Zn2+) and coating agents (Si and Al). NEPs generally released elongated (7-9 × 66-70 nm) and angular (21-80 × 25-79 nm) nTiO2, near-spherical (12-49 nm) and angular nAg (21-76 × 29-77 nm), and angular nZnO (32-36 × 32-40 nm). NEPs released varying ENMs' total concentrations (ca 0.4-95%) of total Ti, Ag, Ag+, Zn, and Zn2+ relative to the initial amount of ENMs added in NEPs, influenced by the nature of the product and recipient water quality. The findings confirmed the use of the examined NEPs as sources of nanopollution in water resources, and the physicochemical properties of the nanopollutants were determined. Exposure assessment data from real-life sources are highly valuable for enriching the robust environmental risk assessment of nanotechnology.

Interactions of Coated-Gold Engineered Nanoparticles with Aquatic Higher Plant Salvinia minima Baker.

The study investigated the interactions of coated-gold engineered nanoparticles (nAu) with the aquatic higher plant Salvinia minima Baker in 2,7, and 14 d. Herein, the nAu concentration of 1000 µg/L was used; as in lower concentrations, analytical limitations persisted but >1000 µg/L were deemed too high and unlikely to be present in the environment. Exposure of S. minima to 1000 µg/L of citrate (cit)- and branched polyethyleneimine (BPEI)-coated nAu (5, 20, and 40 nm) in 10% Hoagland's medium (10 HM) had marginal effect on biomass and growth rate irrespective of nAu size, coating type, or exposure duration. Further, results demonstrated that nAu were adsorbed on the plants' roots irrespective of their size or coating variant; however, no evidence of internalization was apparent, and this was attributed to high agglomeration of nAu in 10 HM. Hence, adsorption was concluded as the basic mechanism of nAu accumulation by S. minima. Overall, the long-term exposure of S. minima to nAu did not inhibit plant biomass and growth rate but agglomerates on plant roots may block cell wall pores, and, in turn, alter uptake of essential macronutrients in plants, thus potentially affecting the overall ecological function.

Aquatic Environment Exposure and Toxicity of Engineered Nanomaterials Released from Nano-Enabled Products: Current Status and Data Needs.

Rapid commercialisation of nano-enabled products (NEPs) elevates the potential environmental release of engineered nanomaterials (ENMs) along the product life cycle. The current review examined the state of the art literature on aquatic environment exposure and ecotoxicity of product released (PR) engineered nanomaterials (PR-ENMs). Additionally, the data obtained were applied to estimate the risk posed by PR-ENMs to various trophic levels of aquatic biota as a means of identifying priority NEPs cases that may require attention with regards to examining environmental implications. Overall, the PR-ENMs are predominantly associated with the matrix of the respective NEPs, a factor that often hinders proper isolation of nano-driven toxicity effects. Nevertheless, some studies have attributed the toxicity basis of observed adverse effects to a combination of the released ions, ENMs and other components of NEPs. Notwithstanding the limitation of current ecotoxicology data limitations, the risk estimated herein points to an elevated risk towards fish arising from fabrics' PR-nAg, and the considerable potential effects from sunscreens' PR-nZnO and PR-nTiO2 to algae, echinoderms, and crustaceans (PR-nZnO), whereas PR-nTiO2 poses no significant risk to echinoderms. Considering that the current data limitations will not be overcome immediately, we recommend the careful application of similar risk estimation to isolate/prioritise cases of NEPs for detailed characterisation of ENMs' release and effects in aquatic environments.

Interactions of metal-based engineered nanoparticles with aquatic higher plants: A review of the state of current knowledge.

The rising potential for the release of engineered nanoparticles (ENPs) into aquatic environments requires evaluation of risks to protect ecological health. The present review examines knowledge pertaining to the interactions of metal-based ENPs with aquatic higher plants, identifies information gaps, and raises considerations for future research to advance knowledge on the subject. The discussion focuses on ENPs' bioaccessibility; uptake, adsorption, translocation, and bioaccumulation; and toxicity effects on aquatic higher plants. An information deficit surrounds the uptake of ENPs and associated dynamics, because the influence of ENP characteristics and water quality conditions has not been well documented. Dissolution appears to be a key mechanism driving bioaccumulation of ENPs, whereas nanoparticulates often adsorb to plant surfaces with minimal internalization. However, few reports document the internalization of ENPs by plants; thus, the role of nanoparticulates' internalization in bioaccumulation and toxicity remains unclear, requiring further investigation. The toxicities of metal-based ENPs mainly have been associated with dissolution as a predominant mechanism, although nano toxicity has also been reported. To advance knowledge in this domain, future investigations need to integrate the influence of ENP characteristics and water physicochemical parameters, as their interplay determines ENP bioaccessibility and influences their risk to health of aquatic higher plants. Furthermore, harmonization of test protocols is recommended for fast tracking the generation of comparable data. Environ Toxicol Chem 2016;35:1677-1694. © 2016 SETAC.

The oxidative toxicity of Ag and ZnO nanoparticles towards the aquatic plant Spirodela punctuta and the role of testing media parameters.

The toxicity effects of silver (nAg) and zinc oxide (nZnO) engineered nanoparticles (ENPs) on the duckweed Spirodela punctuta were studied to investigate the potential risks posed by these ENPs towards higher aquatic plants. The influence of media abiotic factors on the stability of the ENPs was also evaluated. Marked agglomeration of ENPs was observed after introduction into testing media whereby large particles settled out of suspension and accumulated at the bottom of testing vessels. The high ionic strength (IS) promoted agglomeration of ENPs because it reduced the inter-particle repulsion caused by a reduction in their surface charge. Low dissolution was observed for nAg, reaching only 0.015% at 1000 mg L(-1), whilst improved dissolution was observed for nZnO, only falling below analytical quantification at 0.1 mg L(-1) and lower. The quantification of free radicals namely, reactive oxygen and nitrogen species (ROS/RNS) and hydrogen peroxide (H2O2), indicated the induction of oxidative stress in plants exposed to the ENPs. A definite dose influence was observed for ROS/RNS volumes in plants exposed to nZnO for 14 days, a response not always observed. The total antioxidant capacity (TAC) and superoxide dismutase (SOD) activity in plants indicated varying degrees of oxidative toxicity caused by exposure to ENPs. This toxicity was driven mainly by particulates in plants exposed to nAg, whilst dissolved Zn(2+) was the main driver for toxicity in plants exposed to nZnO. Our findings suggest that the toxicity of nAg and nZnO could be caused by both the particulates and ionic forms, as modified by media properties.