Aging of Copper Nanoparticles in the Marine Environment Regulates Toxicity for a Coastal Phytoplankton Species.

Environmental conditions in aquatic ecosystems transform toxic chemicals over time, influencing their bioavailability and toxicity. Using an environmentally relevant methodology, we tested how exposure to seawater for 1-15 weeks influenced the accumulation and toxicity of copper nanoparticles (nano-Cu) in a marine phytoplankton species. Nano-Cu rapidly agglomerated in seawater and then decreased in size due to Cu dissolution. Dissolution rates declined during weeks 1-4 and remained low until 15 weeks, when the large agglomerates that had formed began to rapidly dissolve again. Marine phytoplankton species were exposed for 5-day periods to nano-Cu aged from 1 to 15 weeks at concentrations from 0.01 to 20 ppm. Toxicity to phytoplankton, measured as change in population growth rate, decreased significantly with particle aging from 0 to 4 weeks but increased substantially in the 15-week treatment due apparently to elevated Cu dissolution of reagglomerated particles. Results indicate that the transformation, fate, and toxicity of nano-Cu in marine ecosystems are influenced by a highly dynamic physicochemical aging process.

Fate and Transformation of Graphene Oxide in Estuarine and Marine Waters.

The possibility of graphene oxide (GO) exposure to the environment has spurred several studies investigating the fate of this nanoparticle (NP). However, there is currently little or no data on the fate of GO in estuarine and marine waters. This study investigated the aggregation, sedimentation, and transformation of GO in saline waters, considering the roles of salinity (0-50 ‰), light (visible light and solar irradiation), and aging, among others. The attachment efficiency of GO reached unity at 1.33 ‰. The sedimentation rate of GO increased with salinity up to 10 ‰ after which it decreased due to formation of ramified GO agglomerates and media density. On the basis of the sedimentation rate determined at 30 ‰ (0.121 m/d), the residence time of GO agglomerates in the euphotic zone of typical open oceans will exceed 500 days. Aging in the presence of visible light increased the relative abundance of the GO's aromatic (C-C/C=C) fraction, reducing the NP. Reduction of GO in visible light was confirmed via UV-vis and Raman spectroscopic techniques. Reduction of GO was faster under solar irradiation. This study demonstrates that when introduced into saline waters, GO will undergo a range of transformations affecting its fate and potential effects to aquatic organisms.

Detection and Quantification of Graphene-Family Nanomaterials in the Environment.

An increase in production of commercial products containing graphene-family nanomaterials (GFNs) has led to concern over their release into the environment. The fate and potential ecotoxicological effects of GFNs in the environment are currently unclear, partially due to the limited analytical methods for GFN measurements. In this review, the unique properties of GFNs that are useful for their detection and quantification are discussed. The capacity of several classes of techniques to identify and/or quantify GFNs in different environmental matrices (water, soil, sediment, and organisms), after environmental transformations, and after release from a polymer matrix of a product is evaluated. Extraction and strategies to combine methods for more accurate discrimination of GFNs from environmental interferences as well as from other carbonaceous nanomaterials are recommended. Overall, a comprehensive review of the techniques available to detect and quantify GFNs are systematically presented to inform the state of the science, guide researchers in their selection of the best technique for the system under investigation, and enable further development of GFN metrology in environmental matrices. Two case studies are described to provide practical examples of choosing which techniques to utilize for detection or quantification of GFNs in specific scenarios. Because the available quantitative techniques are somewhat limited, more research is required to distinguish GFNs from other carbonaceous materials and improve the accuracy and detection limits of GFNs at more environmentally relevant concentrations.

Metabolomics Reveals Cu(OH)2 Nanopesticide-Activated Anti-oxidative Pathways and Decreased Beneficial Antioxidants in Spinach Leaves.

While the use of nanopesticides in modern agriculture continues to increase, their effects on crop plants are still poorly understood. Here, 4 week old spinach plants grown in an artificial medium were exposed via foliar spray to Cu(OH)2 nanopesticide (0.18 and 18 mg/plant) or Cu ions (0.15 and 15 mg/plant) for 7 days. A gas chromatography-time-of-flight-mass spectrometry metabolomics approach was applied to assess metabolic alterations induced by Cu(OH)2 nanopesticide in spinach leaves. Exposure to Cu(OH)2 nanopesticide and copper ions induced alterations in the metabolite profiles of spinach leaves. Compared to the control, exposure to 18 mg of Cu(OH)2 nanopesticide induced significant reduction (29-85%) in antioxidant or defense-associated metabolites including ascorbic acid, α-tocopherol, threonic acid, ß-sitosterol, 4-hydroxybutyric acid, ferulic acid, and total phenolics. The metabolic pathway for ascorbate and aldarate was disturbed in all exposed spinach plants (nanopesticide and Cu2+). Cu2+ is responsible for the reduction in antioxidants and perturbation of the ascorbate and aldarate metabolism. However, nitrogen metabolism perturbation was nanopesticide-specific. Spinach biomass and photosynthetic pigments were not altered, indicating that metabolomics can be a rapid and sensitive tool for the detection og earlier nanopesticide effects. Consumption of antioxidants during the antioxidant defense process resulted in reduction of the nutritional value of exposed spinach.

Interactions between Algal Extracellular Polymeric Substances and Commercial TiO2 Nanoparticles in Aqueous Media.

The implications of engineered nanomaterials (ENMs) in the environment are often investigated using pristine particles. However, there are several biogenic and geogenic materials in natural waters that interact with and modify the surface of ENMs, thereby influencing their fate and effects. Here we studied the influence of soluble extracellular polymeric substances (sEPS) produced by freshwater and marine algae on the surface properties and fate of three commercial TiO2 nanoparticles (nTiO2) with different coatings. Adsorption of sEPS by the various nTiO2 is dependent on particle surface area, intrinsic nTiO2 surface charge, and hydrophobicity. Interactions between sEPS and nTiO2 were driven by electrostatic interactions and chemical bonding (bridge-coordination) between the COO- group of sEPS and nTiO2. Charge reversal of positively charged nTiO2 was observed at pH 7 in the presence of 0.5 mg-C/L sEPS. In addition, the critical coagulation concentration (CCC) of nTiO2 increased in the presence of sEPS-from both freshwater and marine sources. CCC of all nTiO2 increased as sEPS concentrations increased. This study shows that naturally occurring sEPS can modify the surface properties and fate of nTiO2 in natural waters, and should be accounted for when predicting the fate and effects of engineered nanomaterials in the environment.

Metabolomics to Detect Response of Lettuce (Lactuca sativa) to Cu(OH)2 Nanopesticides: Oxidative Stress Response and Detoxification Mechanisms.

There has been an increasing influx of nanopesticides into agriculture in recent years. Understanding the interaction between nanopesticides and edible plants is crucial in evaluating the potential impact of nanotechnology on the environment and agriculture. Here we exposed lettuce plants to Cu(OH)2 nanopesticides (1050-2100 mg/L) through foliar spray for one month. Inductively coupled plasma-mass spectrometry (ICP-MS) results indicate that 97-99% (1353-2501 mg/kg) of copper was sequestered in the leaves and only a small percentage (1-3%) (17.5-56.9 mg/kg) was translocated to root tissues through phloem loading. Gas chromatography-time-of-flight mass spectrometry (GC-TOF-MS) based metabolomics combined with partial least squares-discriminant analysis (PLS-DA) multivariate analysis revealed that Cu(OH)2 nanopesticides altered metabolite levels of lettuce leaves. Tricarboxylic (TCA) cycle and a number of amino acid-related biological pathways were disturbed. Some antioxidant levels (cis-caffeic acid, chlorogenic acid, 3,4-dihydroxycinnamic acid, dehydroascorbic acid) were significantly decreased compared to the control, indicating that oxidative stress and a defense response occurred. Nicotianamine, a copper chelator, increased by 12-27 fold compared to the control, which may represent a detoxification mechanism. The up-regulation of polyamines (spermidine and putrescine) and potassium may mitigate oxidative stress and enhance tolerance. The data presented here provide a molecular-scale perspective on the response of plants to copper nanopesticides.

Influence of Phytoplankton on Fate and Effects of Modified Zerovalent Iron Nanoparticles.

Nanoscale zerovalent iron (nZVI) and its derivatives hold promise for remediation of several pollutants but their environmental implications are not completely clear. In this study, the physicochemical properties and aggregation kinetics of sulfide/silica-modified nZVI (FeSSi) were compared in algal media in which Chlamydomonas reinhardtii had been cultured for 1, 2, or 11 days in order to elicit the effects of organic matter produced by the freshwater algae. Furthermore, transformation of FeSSi particles were investigated in C. reinhardtii cultures in exponential (1-d) and slowing growth (11-d) phases while monitoring the response of algae. We found evidence for steric stabilization of FeSSi by algal organic matter, which led to a decrease in the particles' attachment efficiency. Transformation of FeSSi was slower in 11-d cultures as determined via inductively coupled plasma and X-ray analyses. High concentrations of FeSSi caused a lag in algal growth, and reduction in steady state population size, especially in cultures in exponential phase. The different outcomes are well described by a dynamic model describing algal growth, organic carbon production, and FeSSi transformations. This study shows that feedback from algae may play important roles in the environmental implications of engineered nanomaterials.

(1)H NMR and GC-MS Based Metabolomics Reveal Defense and Detoxification Mechanism of Cucumber Plant under Nano-Cu Stress.

Because copper nanoparticles are being increasingly used in agriculture as pesticides, it is important to assess their potential implications for agriculture. Concerns have been raised about the bioaccumulation of nano-Cu and their toxicity to crop plants. Here, the response of cucumber plants in hydroponic culture at early development stages to two concentrations of nano-Cu (10 and 20 mg/L) was evaluated by proton nuclear magnetic resonance spectroscopy ((1)H NMR) and gas chromatography-mass spectrometry (GC-MS) based metabolomics. Changes in mineral nutrient metabolism induced by nano-Cu were determined by inductively coupled plasma-mass spectrometry (ICP-MS). Results showed that nano-Cu at both concentrations interferes with the uptake of a number of micro- and macro-nutrients, such as Na, P, S, Mo, Zn, and Fe. Metabolomics data revealed that nano-Cu at both levels triggered significant metabolic changes in cucumber leaves and root exudates. The root exudate metabolic changes revealed an active defense mechanism against nano-Cu stress: up-regulation of amino acids to sequester/exclude Cu/nano-Cu; down-regulation of citric acid to reduce the mobilization of Cu ions; ascorbic acid up-regulation to combat reactive oxygen species; and up-regulation of phenolic compounds to improve antioxidant system. Thus, we demonstrate that nontargeted (1)H NMR and GC-MS based metabolomics can successfully identify physiological responses induced by nanoparticles. Root exudates metabolomics revealed important detoxification mechanisms.

Aggregation, dissolution, and transformation of copper nanoparticles in natural waters.

Time-dependent aggregation, sedimentation, dissolution, and transformation of three copper-based engineered nanomaterials (ENMs) of varied properties were measured in eight natural and artificial waters. Nano-Cu and Cu(OH)2 aggregated rapidly to >10(3) nm while the aggregate size of nano-CuO averaged between 250 and 400 nm. Aggregate size for both nano-Cu and nano-CuO showed a positive correlation with ionic strength with a few exceptions. Aggregate size did not correlate well with sedimentation rate, suggesting sedimentation was influenced by other factors. Controlling factors in sedimentation rates varied by particle: Cu(OH)2 particles remained stable in all waters but groundwater, nano-Cu was generally unstable except in waters with high organic content, and nano-CuO was stabilized by the presence of phosphate, which reversed surface charge polarity at concentrations as low as 0.1 mg PO4(3-) L(-1). Dissolution generally correlated with pH, although in saline waters, dissolved copper formed insoluble complexes. Nano-Cu was rapidly oxidized, resulting in dissolution immediately followed by the formation of precipitates. These results suggest factors including phosphate, carbonate, and ENM oxidation state may be key in determining Cu ENM behavior in natural waters.

Influence of extracellular polymeric substances on the long-term fate, dissolution, and speciation of copper-based nanoparticles.

The influence of phytoplankton-derived soluble extracellular polymeric substances (EPS), pH, and ionic strength (IS) on the dissolution, speciation, and stability of nano-CuO, nano-Cu, and Kocide (a micron sized Cu(OH)2-based fungicide) was investigated over 90 days. EPS improved the stability of commercial copper-based nanoparticles (CBNPs) in most conditions, in addition to influencing their dissolution. The dissolution rate was pH 4≫pH 7>pH 11. The presence of EPS correlated with higher dissolved Cu at pH 7 and 11, and lower dissolved Cu at pH 4. More dissolution was observed at higher IS (NaCl) due to complexation with Cl-. Dissolution of nano-CuO at pH 7 increased from 0.93% after 90 days (without EPS) to 2.01% (with 5 mg-C EPS/L) at 10 mM IS. Nano-CuO dissolved even more (2.42%) when IS was increased to 100 mM NaCl (with EPS). The ratio of free-Cu2+/total dissolved Cu decreased in the presence of EPS, or as pH and/or IS increased. On a Cu mass basis, Kocide had the highest dissolved and suspended Cu at pH 7. However, dissolution of nano-Cu resulted in a higher fraction of free Cu2+, which may make nano-Cu more toxic to pelagic organisms.

Effects of TiO2 and Ag nanoparticles on polyhydroxybutyrate biosynthesis by activated sludge bacteria.

Manufactured nanomaterials (MNMs) are increasingly incorporated into consumer products that are disposed into sewage. In wastewater treatment, MNMs adsorb to activated sludge biomass where they may impact biological wastewater treatment performance, including nutrient removal. Here, we studied MNM effects on bacterial polyhydroxyalkanoate (PHA), specifically polyhydroxybutyrate (PHB), biosynthesis because of its importance to enhanced biological phosphorus (P) removal (EBPR). Activated sludge was sampled from an anoxic selector of a municipal wastewater treatment plant (WWTP), and PHB-containing bacteria were concentrated by density gradient centrifugation. After starvation to decrease intracellular PHB stores, bacteria were nutritionally augmented to promote PHB biosynthesis while being exposed to either MNMs (TiO2 or Ag) or to Ag salts (each at a concentration of 5 mg L(-1)). Cellular PHB concentration and PhyloChip community composition were analyzed. The final bacterial community composition differed from activated sludge, demonstrating that laboratory enrichment was selective. Still, PHB was synthesized to near-activated sludge levels. Ag salts altered final bacterial communities, although MNMs did not. PHB biosynthesis was diminished with Ag (salt or MNMs), indicating the potential for Ag-MNMs to physiologically impact EBPR through the effects of dissolved Ag ions on PHB producers.

Adsorption of PFAS onto secondary microplastics: A mechanistic study.

Microplastics (MPs) are abundant in aquatic systems. The ecological risks of MPs may arise from their physical features, chemical properties, and/or their ability to concentrate and transport other contaminants, such as per- and polyfluoroalkyl substances (PFAS). PFAS have been extracted from MPs found in natural waters. Still, there needs to be a mechanistic investigation of the effect of PFAS chemistry and water physicochemical properties on how PFAS partition onto secondary MPs. Here, we studied the influence of pH, natural organic matter (NOM), ionic strength, and temperature on the adsorption of PFAS on MPs generated from PET water bottles. The adsorption of PFAS to the MPs was thermodynamically spontaneous at 25 °C, based on Gibb's free energy (ΔG = -16 to -23 kJ/mol), primarily due to increased entropy after adsorption. Adsorption reached equilibrium within 7-9 h. Hence, PFAS will partition to the surface of secondary PET MPs within hours in fresh and saline waters. Natural organic matter decreased the capacity of secondary PET MPs for PFAS through electrosteric repulsion, while higher ionic strength favored PFAS adsorption by decreasing electrostatic repulsion. Increased pH increased electrostatic repulsion, which negated PFAS adsorption. The study provides fundamental information for developing models to predict interactions between secondary MPs and PFAS.

PFAS release from the subsurface and capillary fringe during managed aquifer recharge.

Managed aquifer recharge (MAR) is a sustainable way of harvesting groundwater in water-stressed urbanized areas, where reclaimed wastewater or stormwater is applied on a large basin to infiltrate water into the groundwater aquifer naturally. This process could rapidly fluctuate the water table and move the capillary fringe boundary, and the change in flow dynamic and associated geochemical changes could trigger the release of sequestered pollutants, including per- and polyfluoroalkyl substances (PFAS), also known as 'forever chemicals', from the subsurface and capillary fringe. Yet, the potential of PFAS release from the subsurface and capillary zone during recharge events when the water table rapidly fluctuates has not been evaluated. This study uses laboratory column experiments to simulate PFAS release from pre-contaminated subsurface and capillary fringe during groundwater table fluctuation. The results reveal that the groundwater level fluctuations during MAR increased the release of perfluorobutanesulfonic acid (PFBS) and perfluorooctanesulfonic acid (PFOS) from the capillary fringe, but the fraction released depended on PFAS type and their association with soil colloids. A higher proportion of PFOS in column effluent was found to be associated with particles, while a greater portion of released PFBS was in a free or dissolved state. The direction of water table fluctuation did not affect the release of PFAS in this study. A lack of change in the concentration of bromide, a conservative tracer, during flow interruption, indicates that diffusion of PFAS through reconnected pores during water table rise had an insignificant effect on PFAS release. Overall, this study provides insights into how PFAS can be released from the subsurface and capillary fringe during managed aquifer recharge when the groundwater level is expected to fluctuate quickly.

Elimination of microplastics, PFAS, and PPCPs from biosolids via pyrolysis to produce biochar: Feasibility and techno-economic analysis.

Biosolids from municipal wastewater treatment contain many contaminants of emerging concern, including microplastics (MPs), per- and polyfluoroalkyl substances (PFAS), pharmaceuticals and chemicals from personal care products (PPCPs). Many of these contaminants have very slow biotic or abiotic degradation rates and have been shown to have human and ecological health impacts. Application of biosolids to agriculture, a common disposal method, can result in extended environmental contamination. An approach for eliminating the contaminants is pyrolysis, which can also generate biochar, enhancing carbon sequestration as a side-benefit. We pyrolyzed biosolid samples from an operating facility at various temperatures from 400 to 700 °C with a 2-hour residence time. We then evaluated contaminant removal, which in many cases was 100 %, with only a few residuals. No trace of PFAS was detectable even at 400 °C. Overall mass removal of PPCPs, including PFAS, was over 99.9 %. MP removal via pyrolysis ranged from 91 to 97 %. The biochar contains significant amounts of Fe and P, which make it a useful fertilizer amendment. The techno-economic analysis indicates that pyrolysis may generate significant cost savings, and revenue from the sale of biochar, sufficient to more than cover the investment and operating costs of the dryer and pyrolysis unit.

Perfluorooctanoic acid dominates the molecular-level effects of a mixture of equal masses of perfluorooctanoic acid and perfluorooctane sulfonic acid in earthworm.

Per- and polyfluoroalkyl substances (PFAS) are an important class of emerging contaminants in the environment. Most studies on the impact of PFAS mixtures considered phenotypic endpoints, which may not adequately reflect the sublethal effects on organisms. To fill this knowledge gap, we investigated the subchronic impact of environmentally relevant concentrations of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS)-as individual compounds and a mixture (PFOS+PFOA)-on earthworm (Eisenia fetida), using phenotypic and molecular endpoints. PFAS decreased the survival (12.2-16.3%), biomass (9.0-9.8%), and reproduction (15.6-19.8%) of E. fetida after 28 d of exposure. The bioaccumulation of PFOS after 28 d increased (from 2790.7 ng/g-dw to 5224.9 ng/g-dw) while that of PFOA decreased (from 780.2 ng/g-dw to 280.5 ng/g-dw) when E. fetida was exposed to the mixture compared to the individual compounds. These bioaccumulation trends were partly attributed to changes in the soil distribution coefficient (Kd) of PFOS and PFOA when present in the mixture. Eighty percent of the (p and FDR < 0.05) altered metabolites after 28 d were similarly perturbed by both PFOA and PFOS+PFOA. The pathways dysregulated are related to the metabolism of amino acids, energy, and sulfur. We showed that PFOA dominates the molecular-level impact of the binary PFAS mixture.

Nanomaterials as catalysts for CO2 transformation into value-added products: A review.

Carbon dioxide (CO2) is the most important greenhouse gas (GHG), accounting for 76% of all GHG emissions. The atmospheric CO2 concentration has increased from 280 ppm in the pre-industrial era to about 418 ppm, and is projected to reach 570 ppm by the end of the 21st century. In addition to reducing CO2 emissions from anthropogenic activities, strategies to adequately address climate change must include CO2 capture. To promote circular economy, captured CO2 should be converted to value-added materials such as fuels and other chemical feedstock. Due to their tunable chemistry (which allows them to be selective) and high surface area (which allows them to be efficient), engineered nanomaterials are promising for CO2 capturing and/or transformation. This work critically reviewed the application of nanomaterials for the transformation of CO2 into various fuels, like formic acid, carbon monoxide, methanol, and ethanol. We discussed the literature on the use of metal-based nanomaterials, inorganic/organic nanocomposites, as well as other routes suitable for CO2 conversion such as the electrochemical, non-thermal plasma, and hydrogenation routes. The characteristics, steps, mechanisms, and challenges associated with the different transformation technologies were also discussed. Finally, we presented a section on the outlook of the field, which includes recommendations for how to continue to advance the use of nanotechnology for conversion of CO2 to fuels.

Shrimp waste-derived porous carbon adsorbent: Performance, mechanism, and application of machine learning.

Aquaculture generates significant amount of processing wastes (more than 500 million pounds annually in the United States), the bulk of which ends up in the environment or is used in animal feed. Proper utilization of shrimp waste can increase their economic value and divert them from landfills. In this study, shrimp waste was converted to a porous carbon (named SPC) via direct pyrolysis and activation. SPC was characterized, and its performance for adsorbing ciprofloxacin from simulated water, natural waters, and wastewater was benchmarked against a commercial powdered activated carbon (PAC). The surface area of SPC (2262 m2/g) exceeded that of PAC (984 m2/g) due to abundance of micropores and mesopores. The adsorption of ciprofloxacin by SPC was thermodynamically spontaneous (ΔG = -19 kJ/mol) and fast (k1 = 1.05/min) at 25 °C. The capacity of SPC for ciprofloxacin (442 mg/g) was higher than that of PAC (181 mg/g). SPC also efficiently and simultaneously removed low concentrations (200 µg/L) of ciprofloxacin, long-chain per- and polyfluoroalkyl substances (PFAS), and Cu ions from water. An artificial neural network function was derived to predict ciprofloxacin adsorption and identify the relative contribution of each input parameter. This study demonstrates a sustainable and commercially viable pathway to reuse shrimp processing wastes.

Removal of tetracycline by aerobic granular sludge from marine aquaculture wastewater: A molecular dynamics investigation.

Although biological treatment of marine aquaculture wastewater is promising, the fundamental principles driving the adsorption of tetracycline to microbial cell membrane are not well understood. Using a combination of experiments and molecular dynamics (MD) simulations, the mechanism underlying the biological removal of tetracycline from seawater was investigated. More than 90% tetracycline removal was achieved in an aerobic granular sludge system, with degradation accounting for 30% of total removal. A model of the tetracycline-dipalmitoylphosphatidylcholine lipid bilayers was established to elucidate the transport mechanism of tetracycline from bulk solution to microorganisms' cell membrane. 62% of the driving force for tetracycline adsorption on the cell membrane originated from electrostatic attraction. The electrophilic groups on tetracycline (amino and aromatic groups) were attracted to the phosphate groups in the cell membrane. Sodium ions, which are abundant in seawater, decreased the interaction energy between tetracycline and the cell membrane.

Effects of WS2 Nanosheets on N2-fixing Cyanobacteria: ROS overproduction, cell membrane damage, and cell metabolic reprogramming.

The ecotoxicity of tungsten disulfide (WS2) nanomaterials remains unclear so far. Here, the toxicity of WS2 nanosheets on N2-fixing cyanobacteria (Nostoc sphaeroides) was evaluated. Specifically, Nostoc were cultivated in media spiked with different concentrations of WS2 nanosheets (0, 0.05, 0.1 and 0.5 mg/L) for 96 h. Relative to unexposed cells, WS2 nanosheets at 0.5 mg/L significantly decreased cell density, content of total sugar and protein by 10.9 %, 0.43 %, and 6.1 %, respectively. Gas chromatography-mass spectrometry (GC-MS)-based metabolomics revealed that WS2 nanosheets exposure altered the metabolite profile of Nostoc in a dose-dependent manner. Energy metabolism related pathways, including the Calvin-Benson-Bassham (CBB) cycle and tricarboxylic acid (TCA) cycle, were significantly inhibited. In addition, WS2 nanosheets exposure resulted in downregulation (20-40 %) of S-containing amino acids (cystine, methionine, and cysteine) and sulfuric acid. Additionally, fatty acids and antioxidant-related compounds (formononetin, catechin, epigallocatechin, dehydroascorbic acid, and alpha-tocopherol) in Nostoc were drastically decreased by 4-50 % upon exposure to WS2 nanosheets, which implies oxidative stress induced by the nanomaterials. Biochemical assays for reactive oxygen species (ROS) and malondialdehyde (MDA) confirmed that WS2 nanosheets triggered ROS overproduction and induced lipid peroxidation. Taken together, WS2 exposure perturbed carbon (C), nitrogen (N), and sulfate (S) metabolism of Nostoc, which may influence C, N, and S cycling, given the important roles of cyanobacteria in these processes. These results highlight the need for caution in the application and environmental release of WS2 nanomaterials to prevent unintended environmental impacts due to their potential ecotoxicity.

Assessing the Environmental Effects Related to Quantum Dot Structure, Function, Synthesis and Exposure.

Quantum dots (QDs) are engineered semiconductor nanocrystals with unique fluorescent, quantum confinement, and quantum yield properties, making them valuable in a range of commercial and consumer imaging, display, and lighting technologies. Production and usage of QDs are increasing, which increases the probability of these nanoparticles entering the environment at various phases of their life cycle. This review discusses the major types and applications of QDs, their potential environmental exposures, fates, and adverse effects on organisms. For most applications, release to the environment is mainly expected to occur during QD synthesis and end-product manufacturing since encapsulation of QDs in these devices prevents release during normal use or landfilling. In natural waters, the fate of QDs is controlled by water chemistry, light intensity, and the physicochemical properties of QDs. Research on the adverse effects of QDs primarily focuses on sublethal endpoints rather than acute toxicity, and the differences in toxicity between pristine and weathered nanoparticles are highlighted. A proposed oxidative stress adverse outcome pathway framework demonstrates the similarities among metallic and carbon-based QDs that induce reactive oxygen species formation leading to DNA damage, reduced growth, and impaired reproduction in several organisms. To accurately evaluate environmental risk, this review identifies critical data gaps in QD exposure and ecological effects, and provides recommendations for future research. Future QD regulation should emphasize exposure and sublethal effects of metal ions released as the nanoparticles weather under environmental conditions. To date, human exposure to QDs from the environment and resulting adverse effects has not been reported.