Characterization of Fe-Containing and Pb-Containing Nanoparticles Resulting from Corrosion of Plumbing Materials in Tap Water Using a Hyphenated ATM-DMA-spICP-MS System.

Single-particle inductively coupled plasma mass spectrometry (spICP-MS) has been used to characterize metallic nanoparticles (NPs) assuming that all NPs are spherical and composed of pure element. However, environmental NPs generally do not meet these criteria, suggesting that spICP-MS may underestimate their true sizes. This study employed a system hyphenating the atomizer (ATM), differential mobility analyzer (DMA), and spICP-MS to characterize metallic NPs in tap water. Its performance was validated by using reference Au nanoparticles (AuNPs) and Ag-shelled AuNPs. The hyphenated system can determine the actual size and metal composition of both NPs with additional heating after ATM, while stand-alone spICP-MS misidentified the Ag-shelled AuNPs as smaller individual AgNPs and AuNPs. Dissolved metal ions could introduce artifact NPs after heating but could be eliminated by centrifugation. The hyphenated system was applied to characterize Fe-containing and Pb-containing NPs resulting from the corrosion of plumbing materials in tap water. The mode sizes of Fe-containing and Pb-containing NPs were determined to be 110 and 100 nm and the particle number concentrations were determined to be 4.99 × 107 and 1.40 × 106 #/mL, respectively. Cautions should be paid to potential changes in particle size induced by heating for metallic NPs with a low melting point or a high organic content.

Dissolution behavior of ZnO nanoparticles at environmentally relevant low concentrations in surface waters: Equilibrium and kinetics.

Environmentally relevant fate parameters are essential in accurate prediction of nanomaterial's exposure. This study investigates the dissolution kinetics and equilibrium of ZnO nanoparticles (ZnONPs) using environmentally relevant low concentrations (50-200 µg/L) of ZnONPs in river water and lake water samples, and a seawater-influenced river water. We found that ZnONPs at an initial concentration of 50 µg/L completely dissolved independent of water matrices, while at 100 and 200 µg/L the dissolution level of ZnONPs was strongly dependent on the water chemistry. Carbonate alkalinity was found to control the dissolution levels, and can react with dissolved Zn ion to form secondary solid product hydrozincite. An analysis of our kinetic data and comprehensive literature results reveals that the dissolution kinetic coefficients largely increased with decreased initial ZnONP concentrations especially in environmental water matrices. The result highlights the importance to measure and derive representative dissolution parameters of nanomaterials using environmentally relevant concentrations.

Toxicity prediction: An application of alternative testing and computational toxicology in contaminated groundwater sites in Taiwan.

Groundwater contamination remains a global threat due to its toxic effects to humans and the environment. The remediation of contaminated groundwater sites can be costly, thus, identifying the priority areas of concern is important to reduce money spent on resources. In this study, we aimed to identify and rank the priority groundwater sites in a contaminated petrochemical district by combining alternative, non-animal approaches - chemical analysis, cell-based high throughput screening (HTS), and Toxicological Priority Index (ToxPi) computational toxicology tool. Groundwater samples collected from ten different sites in a contaminated district showed pollutant levels below the detection limit, however, hepatotoxic bioactivity was demonstrated in human hepatoma HepaRG cells. Integrating the pollutants information (i.e., pollutant characteristics and concentration data) with the bioactivity data of the groundwater samples, an evidence-based ranking of the groundwater sites for future remediation was established using ToxPi analysis. The currently presented combinatorial approach of screening groundwater sites for remediation purposes can further be refined by including relevant parameters, which can boost the utility of this approach for groundwater screening and future remediation.

A two-dimensional nanoparticle characterization method combining differential mobility analyzer and single-particle inductively coupled plasma-mass spectrometry with an atomizer-enabled sample introduction (ATM-DMA-spICP-MS): Toward the analysis of heteroaggregated nanoparticles in wastewater.

Characterizing engineered nanoparticles (ENPs) in complex environmental matrices remains a challenging task. This work presents a two-dimensional size analysis method by combining differential mobility analyzer (DMA) and single-particle inductively coupled plasma-mass spectrometry (spICP-MS) with a new atomizer (ATM)-enabled sample introduction that is relatively easy to operate. The tailing of electrical mobility size distributions was solved by heating the aerosol flow, where water-shelled gold nanoparticles (AuNPs) were dehydrated, effectively eliminating the tailing. The improved method has a good sizing performance and can resolve the size fractions of mixed 30 nm and 50 nm AuNPs. It can reliably analyze 7.8 × 105 to 1.9 × 107 # of 50 nm AuNPs (or 4.1 × 105 to 107 # NPs/mL, equivalent to 0.6 to 14.3 µg Au/L) with a linear response and a limit of detection of 7.8 × 105 # AuNPs (equivalent to 4.1 × 105 # AuNPs/mL) that is relevant to NP concentrations in surface water and wastewater samples. The potential of this method to analyze environmental samples was demonstrated by characterizing AuNPs and silver nanoparticles (AgNPs) spiked in wastewater, where both NPs were revealed to form heteroaggregates with colloids existing in wastewater. The method can even directly analyze nanosized Ag particles inherent in the wastewater before adding external AgNPs. The result indicates that ATM-DMA-spICP-MS is a relatively simple two-dimensional size analysis method that has a great potential to characterize heteroaggregated NPs in aqueous environmental samples.

The Impact of Background-Level Carboxylated Single-Walled Carbon Nanotubes (SWCNTs-COOH) on Induced Toxicity in Caenorhabditis elegans and Human Cells.

Single-walled carbon nanotubes (SWCNTs) are widely utilized for industrial, biomedical, and environmental purposes. The toxicity of Carboxylated SWCNTs (SWCNTs-COOH) in in vivo models, particularly Caenorhabditis elegans (C. elegans), and in vitro human cells is still unclear. In this study, C. elegans was used to study the effects of SWCNTs-COOH on lethality, lifespan, growth, reproduction, locomotion, reactive oxygen species (ROS) generation, and the antioxidant system. Our data show that exposure to ≥1 µg·L-1 SWCNTs-COOH could induce toxicity in nematodes that affects lifespan, growth, reproduction, and locomotion behavior. Moreover, the exposure of nematodes to SWCNTs-COOH induced ROS generation and the alteration of antioxidant gene expression. SWCNTs-COOH induced nanotoxic effects at low dose of 0.100 or 1.00 µg·L-1, particularly for the expression of antioxidants (SOD-3, CTL-2 and CYP-35A2). Similar nanotoxic effects were found in human cells. A low dose of SWCNTs-COOH induced ROS generation and increased the expression of catalase, MnSOD, CuZnSOD, and SOD-2 mRNA but decreased the expression of GPX-2 and GPX-3 mRNA in human monocytes. These findings reveal that background-level SWCNTs-COOH exerts obvious adverse effects, and C. elegans is a sensitive in vivo model that can be used for the biological evaluation of the toxicity of nanomaterials.

Bioaccumulation and depuration of TiO2 nanoparticles by zebrafish through dietary exposure: Size- and number concentration-resolved analysis using single-particle ICP-MS.

The bioaccumulation and depuration of TiO2 nanoparticles (TiO2NPs) by zebrafish via the dietary exposure following the OECD Test Guideline 305 (OECD TG305) was evaluated using particle size- and number concentration-resolved analysis based on single-particle ICP-MS (spICP-MS). We found that using enzymatic digestion without H2O2 or excessive heating can recover 84.0 ± 4.0% and 94.5 ± 3.5% of TiO2NP mass and number concentrations from fish tissue, respectively, without altering the size distribution of parent TiO2NPs. OECD TG305 can allow for the evaluation of bioaccumulation and depuration of TiO2NPs by fish based on the particle mass and number dose metrics. The toxicokinetic modeling can reasonably describe the mass- and number-based measurement data with the derived absorption efficiency α at ~0.2, depuration rate at ~0.5 d-1, and kinetic biomagnification factor (BMFk) at ~0.007 comparable with available data. The mass concentration- and number concentration-based bioaccumulation metrics including body burdens are correlated for TiO2NPs that remained nano-sized in vivo and exhibited marginal physicochemical alterations upon uptake by fish. The result indicates that the traditional mass concentration metric may be used to represent the fish bioaccumulation potential for chemically inert NPs like TiO2.

Assessment of the emission factors for potentially toxic elements from coal-fired boilers and sintering furnaces in a steel production plant.

The emission factor (EF), the weight of potentially toxic elements (PTEs) per unit energy or weight of sinter produced were evaluated for coal-fired boilers and sintering furnaces integrated in a steel plant. From three coal-fired boilers, 15 samples were taken while 22 samples were taken from four sintering furnaces. Investigations were performed on the EF of lead, cadmium, mercury, arsenic and chromium (VI). The coefficient of variance for the first 3 samples from each PTE was used to decide whether 2 more samples were necessary for the investigation. Three samples were sufficient for Cr (VI), however, 5 samples were required for Pb, Cd, Hg, and As, since the variances in concentrations of the first three samples exceeded 20%. The ranges for the ratio of the laboratory-based EF to the default EF applied by the Environment Protection Administration (EPA Taiwan) for Pb, Cd, Hg, and As for the coal-fired boiler were 0.08-0.013, 0.014-0.017, 0.019-0.033, 0.047-0.066 and for the sintering furnaces were 0.059-0.232, 0.05-0.151, 0.05-0.364, and 0.067-0.824. The ratio for Cr (VI)- was constant at 0.005 for all the coal fired boilers while it ranged from 0.057-0.709 for the sintering furnaces. Whilst source identification, enrichment factors, and spatial distributions for PTEs are often studied, laboratory-based investigations on the EFs for PTEs from industrial plants are rarely performed. This study filled the information gap and compared the obtained EFs with the EPA default values. To avoid overcharging industrial plants equipped with the best available technology for emission control, the EPA should apply field investigations and laboratory-based EFs instead of the default EPA EFs to calculate air pollution fees. Insights from this investigation can be applied to promote the adoption of appropriate air pollution control devices to cut down the emission of PTEs.

Graphitic carbon nitride embedded with graphene materials towards photocatalysis of bisphenol A: The role of graphene and mediation of superoxide and singlet oxygen.

Composite photocatalysts comprising graphitic carbon nitride (g-C3N4) and graphene materials were synthesized and evaluated in the photocatalysis of bisphenol A (BPA) with a focus on elucidating the reaction mechanism. Embedding reduced graphene oxide (rGO) to g-C3N4 significantly accelerated the photocatalysis rate of BPA by three folds under visible light irradiation at neutral pH. We showed that rGO synthesized in intimate contact with g-C3N4 increased the surface areas and electrical conductivity of the g-C3N4 composites and promoted the electron-hole pair separation. The BPA photodegradation mechanism involved selective oxidants as superoxide (O2•-) and singlet oxygen (1O2) that were formed through one-electron reduction of O2 and the unique oxidation of O2•- by photogenerated hole (h+), respectively. The synthesized photocatalyst exhibited superior visible light photoreactivity to that of N-doped P25 TiO2, good photo-stability and reuse potential, and was operative in complex wastewater. rGO embedded g-C3N4 achieved good photomineralization of BPA at 80% in 4 h compared to 40% of bare g-C3N4. This study sheds light on the photocatalysis mechanism of BPA with a metal-free, promising rGO/g-C3N4 photocatalyst.

Combined impact of silver nanoparticles and chlorine on the cell integrity and toxin release of Microcystis aeruginosa.

Silver nanoparticles (AgNPs) have shown to be toxic to freshwater cyanobacterial species, and sodium hypochlorite (NaOCl) is a common oxidant for the treatment of cyanobacterial cells. AgNPs have a high possibility of co-existing with the cyanobacterial cells in the aqueous environments leading to its exposure to NaOCl during water treatment; however, their combined effects on the cyanobacterial cells are largely undocumented. This work compares the individual and combined effect of AgNP and NaOCl on the integrity and toxin (microcystins) release of Microcystis aeruginosa at varying levels. The results show that the AgNP (0.2-0.6 mg/L) alone has negligible effects on the cell lysis, while NaOCl alone shows concentration-dependent (0.2 < 0.4 < 0.6 mg/L) rupturing of cells. In contrast, the AgNP + NaOCl (0.2-0.6 mg/L) samples show increasing loss in cell integrity at higher AgNP (0.4 and 0.6 mg/L) levels than the NaOCl only samples. NaOCl exposure results in increasing dissolution of AgNPs with time, releasing silver ions (Ag+), affecting its size and morphology. The cell-associated total Ag declines over time with an increase in NaOCl levels, maybe due to increasing cell-lysis or NaOCl induced oxidative dissolution of AgNPs. The cell-associated total Ag and released Ag+ possibly weaken the cellular membrane, thus assisting NaOCl in faster cell-lysis. The combined exposure of AgNP and NaOCl also results in a higher release of toxin from the cells. This work collectively reveals that the AgNPs combined with NaOCl can enhance the cell lysis and release of toxins.

Exposure to ZnO/TiO2 Nanoparticles Affects Health Outcomes in Cosmetics Salesclerks.

Concerns about the effects of nanoparticles (NPs) on human health are being raised by researchers because the risks of nanocosmetics like sunscreen are unknown. We explored the association between urinary oxidative stress markers and exposure of cosmetics salesclerks to 20 cosmetics that might contain titanium dioxide (TiO2)/zinc oxide (ZnO) NPs. We then recruited 40 cosmetics salesclerks and 24 clothing salesclerks and categorized them based on their exposure to ZnO and TiO2 NPs. Nineteen and 15 samples met the EU definition for TiO2 and ZnO nanomaterials, respectively. Participants with a higher co-exposure index of ZnO and TiO2 NPs had a significantly higher base level of urinary 8-hydroxy-2'-deoxyguanosin (8-OHdG) concentrations than the lower co-exposure group (5.82 vs. 2.85 ng/mL, p < 0.001). After potential confounding factors had been adjusted for, the TiO2 and ZnO NP co-exposure index was significantly positively associated with the urinary 8-OHdG base concentration (ß = 0.308, 95% CI = 0.106 to 0.510) and the creatinine-adjusted concentration (ß = 0.486, 95% CI = 0.017 to 0.954). Current evidence suggests that the likelihood of harm from using sunscreens containing nanoparticles might result in higher urinary 8-OHdG. However, our limited number and types of sample cosmetics might underestimate the risk.

A Review on the Environmental Fate Models for Predicting the Distribution of Engineered Nanomaterials in Surface Waters.

Exposure assessment is a key component in the risk assessment of engineered nanomaterials (ENMs). While direct and quantitative measurements of ENMs in complex environmental matrices remain challenging, environmental fate models (EFMs) can be used alternatively for estimating ENMs' distributions in the environment. This review describes and assesses the development and capability of EFMs, focusing on surface waters. Our review finds that current engineered nanomaterial (ENM) exposure models can be largely classified into three types: material flow analysis models (MFAMs), multimedia compartmental models (MCMs), and spatial river/watershed models (SRWMs). MFAMs, which is already used to derive predicted environmental concentrations (PECs), can be used to estimate the releases of ENMs as inputs to EFMs. Both MCMs and SRWMs belong to EFMs. MCMs are spatially and/or temporally averaged models, which describe ENM fate processes as intermedia transfer of well-mixed environmental compartments. SRWMs are spatiotemporally resolved models, which consider the variability in watershed and/or stream hydrology, morphology, and sediment transport of river networks. As the foundation of EFMs, we also review the existing and emerging ENM fate processes and their inclusion in recent EFMs. We find that while ENM fate processes, such as heteroaggregation and dissolution, are commonly included in current EFMs, few models consider photoreaction and sulfidation, evaluation of the relative importance of fate processes, and the fate of weathered/transformed ENMs. We conclude the review by identifying the opportunities and challenges in using EFMs for ENMs.

Roles of Silver-Chloride Complexations in Sunlight-Driven Formation of Silver Nanoparticles.

In aerobic natural surface water, a silver ion (Ag+) exists in various Ag+-Cl- complexes because of a strong affinity for a chloride ion (Cl-); however, little information is available about the role of the Ag+-Cl- complex in the formation of silver nanoparticles (AgNPs). This study demonstrates that soluble AgClx(x-1)- species act as a precursor of AgNPs under simulated sunlight irradiation. The AgNP photoproduction increases with Cl- levels up to 0.0025 M ([Ag+] = 5 × 10-7 M) and decreases with continued Cl- level increase (0.09 to 0.5 M). At [Cl-] ≤ 0.0025 M (freshwater systems), photoproduction of AgNP correlates with the formation of AgCl(aq), suggesting that it is the most photoactive species in those systems. Matching the ionic strength of experiments containing various Cl- levels indicates that the trend in AgNP photoproduction correlates with Cl- concentrations rather than ionic strength-induced effects. The photoproduction of AgNPs is highly pH-dependent, especially at pH > 8.3. The UV and visible light portions of the solar light spectrum are equally important in photoreduction of Ag+. Overall, we show evidence that AgClx(x-1)- species irradiated under sunlight conditions contributes to the formation of nanosized silver (Ag) in the environment.

The impact of low to high waste cooking oil-based biodiesel blends on toxic organic pollutant emissions from heavy-duty diesel engines.

As yet, the effect of biodiesels on the emissions of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) from heavy-duty diesel engines (HDDEs) has only been studied using limited fuel blend ratios. To clarify the influence of using higher fractions of biodiesel on the emissions of toxic organic pollutants from diesel engines, in this research, the emissions of PM, PAHs, and persistent organic pollutants (POPs) from EURO IV and EURO III HDDEs fueled by low to high waste cooking oil (WCO)-based biodiesel-petrodiesel fuel blends were studied, including D100 (0% biodiesel), B20 (20%), B40 (40%), B60 (60%), B80 (80%), and B100 (100%). The engines were tested according to the US FTP-75 test procedure. The results for the EURO IV diesel engine showed that the PM and toxic organic pollutant emissions were reduced with increases in the blending ratio up until the B60 scenario when compared to the D100 scenario. This is because biodiesel has higher oxygen content and no or lower aromatic content than petrodiesel. Nevertheless, during the B80 and B100 scenarios, the PM and toxic organic pollutant emissions increased due to the high viscosity property of biodiesel, which negatively affected the combustion process. The biodiesel effect on the emissions from EURO III engine was more pronounced because of its lower combustion efficiency, and therefore the improvement in combustion using biodiesel resulted in greater PCDD/F reductions.

National surveillance of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins/furans in soil in Taiwan.

In this study, the polychlorinated dibenzo-p-dioxin/furan (PCDD/F) levels in 381 soil samples coming from different background areas (n = 238) and contaminated areas (n = 143) in Taiwan were investigated from 2011 to 2015 using high resolution gas chromatograph/high resolution mass spectrometry (HRGC/HRMS). The contaminated areas showed higher PCDD/F contamination as compared to the background areas (1230 vs 749 pg/g dry weight (dw)); 14.0 vs 6.25 pg WHO2005-TEQ/g dw). The lowest levels were recorded in the outlying islands (1.28 pg WHO2005-TEQ/g dw). PCDD/F congener distribution profiles in the background and contaminated areas as well as on the islands varied. OCDD was the dominant congener in almost all locations, including the northern background (87.7%) and central contaminated (74.2%) areas. Other dominant species included OCDF and 1,2,3,4,6,7,8-HpCDD. Levels of PCDD/F-TEQs in Taiwanese soils, including the background areas, were higher than in some developing countries and regions with global background levels due to high industrialization except for the contaminated areas. Geographic differences in dioxin-contaminated soils were also shown in this study. Higher soil dioxin-TEQs were observed in locations with high populations and population densities. Despite the limitations, the economic status of Taiwan represented by the annual averaged family income (AAFI) was positively correlated to soil dioxin-TEQs.

Photochemical reactivity of aqueous fullerene clusters: C60 versus C70.

Over the past few years, there has been a strong interest in exploring the potential impact of fullerenes in the environment. Despite that both C60 and C70 have been detected in environmental matrices, the research on the impact of higher fullerenes, such as C70, has been largely missing. This study evaluated and compared the phototransformation of aqueous C60 and C70 clusters (nC60 and nC70) and their 1O2 production under sunlight and lamp light irradiation (315nm, 360nm and 420nm). The nC60 and nC70 samples formed by direct mixing with water adopted a face-centered cubic (FCC) crystal structure. The apparent quantum yields (AQYs) of fullerene phototransformed were relatively constant over the examined wavelengths, while 1O2 production AQYs decreased with increased wavelengths. The long-term fate studies with outdoor sunlight indicated that both nC60 and nC70 lost considerable organic carbon contents (>80%) in water after ∼8 months of irradiation and that the intermediate photoproducts of nC60 and nC70 exhibited a progressively increased level of oxygen-containing functionalities. Overall, the study indicates that nC70 can be photochemically removed under sunlight conditions and that the photoreactivity of nC60 based on AQYs is greater than that of nC70.

Phototransformation-Induced Aggregation of Functionalized Single-Walled Carbon Nanotubes: The Importance of Amorphous Carbon.

Single-walled carbon nanotubes (SWCNTs) with proper functionalization are desirable for applications that require dispersion in aqueous and biological environments, and functionalized SWCNTs also serve as building blocks for conjugation with specific molecules in these applications. In this study, we examined the phototransformation of carboxylated SWCNTs and associated amorphous carbon impurities in the presence or absence of H2O2 under simulated sunlight conditions. We found that while carboxylated SWCNTs were rather unreactive with respect to direct solar photolysis, they photoreacted in the presence of H2O2, forming CO2 and strongly aggregated SWCNT products that precipitated. Photoreaction caused SWCNTs to lose oxygen-containing functionalities, and interestingly, the resulting photoproducts had spectral characteristics similar to those of parent carboxylated SWCNTs whose amorphous carbon was removed by base washing. These results indicated that photoreaction of the amorphous carbon was likely involved. The removal of amorphous carbon after indirect photoreaction was confirmed with thermogravimetric analysis (TGA). Further studies using carboxylated SWCNTs with and without base washing indicate that amorphous carbon reduced the extent of aggregation caused by photoreaction. The second-order rate constant for carboxylated SWCNTs reacting with (•)OH was estimated to be in the range of 1.7-3.8 × 10(9) MC(-1) s(-1). The modeled phototransformation half-lives fall in the range of 2.8-280 days in typical sunlit freshwaters. Our study indicates that photosensitized reactions involving (•)OH may be a transformation and removal pathway of functionalized SWCNTs in the aquatic environment, and that the residual amorphous carbon associated with SWCNTs plays a role in SWCNT stabilization.

Sunlight affects aggregation and deposition of graphene oxide in the aquatic environment.

In this study, we investigate the role of simulated sunlight on the physicochemical properties, aggregation, and deposition of graphene oxide (GO) in aquatic environments. Results show that light exposure under varied environmental conditions significantly impacts the physicochemical properties and aggregation/deposition behaviors of GO. Photo-transformation has negligible effects on GO surface charge, however, GO aggregation rates increase with irradiation time for direct photo-transformation under both aerobic and anaerobic conditions. Under anaerobic conditions, photo-reduced GO has a greater tendency to form aggregates than under aerobic conditions. Aggregation of photo-transformed GO is notably influenced by ion valence, with higher aggregation found in the presence of divalent ions versus monovalent, but adding natural organic matter (NOM) reduces it. QCM-D studies show that deposition of GO on surfaces coated with organic matter decreases with increased GO irradiation time, indicating a potential increase in GO mobility due to photo-transformation. General deposition trends on Suwannee River Humic Acid (SRHA)-coated surfaces are control GO > aerobically photo-transformed GO ≈ anaerobically photo-transformed GO. The release of deposited GO from SRHA-coated surfaces decreases with increased irradiation time, indicating that photo-transformed GO is strongly attached to the NOM-coated surface.

Photochemical transformation of graphene oxide in sunlight.

Graphene oxide (GO) is promising in scalable production and has useful properties that include semiconducting behavior, catalytic reactivity, and aqueous dispersibility. In this study, we investigated the photochemical fate of GO under environmentally relevant sunlight conditions. The results indicate that GO readily photoreacts under simulated sunlight with the potential involvement of electron-hole pair creation. GO was shown to photodisproportionate to CO2, reduced materials similar to reduced GO (rGO) that are fragmented compared to the starting material, and low molecular-weight (LMW) species. Kinetic studies show that the rate of the initially rapid photoreaction of GO is insensitive to the dissolved oxygen content. In contrast, at longer time points (>10 h), the presence of dissolved oxygen led to a greater production of CO2 than the same GO material under N2-saturated conditions. Regardless, the rGO species themselves persist after extended irradiation equivalent to 2 months in natural sunlight, even in the presence of dissolved oxygen. Overall, our findings indicate that GO phototransforms rapidly under sunlight exposure, resulting in chemically reduced and persistent photoproducts that are likely to exhibit transport and toxic properties unique from parent GO.

Photoreactivity of unfunctionalized single-wall carbon nanotubes involving hydroxyl radical: chiral dependency and surface coating effect.

Single-wall carbon nanotubes (SWCNTs) have a variety of potential and demonstrated applications, and their production rates are increasing rapidly. This increase in production has motivated research on their transport and potential transformation and their toxicity in the environment. In this work, we examined the direct and indirect photoreactivity of SWCNTs under sunlight conditions. We found that the direct photoreactivity of pristine SWCNTs is generally low; however, indirect photoreaction involving ·OH may be significant in natural aquatic environments. Environmental photochemical reactions generating ·OH lead to distinct changes in SWCNT fluorescence efficiency in the near-infrared (NIR) region, Raman spectra, and light attenuation spectra in the UV, visible, and NIR regions, indicating that covalent functionalization of SWCNTs occurs. The reactivity of SWCNTs to ·OH is dependent on the specific chiral structure of the SWCNTs and the surfactant associated with it. An operationally defined second-order rate constant (based on the decrease in NIR fluorescence signals) for all SWCNT chiral species reacting with ·OH was estimated to be (2.91 ± 1.30) × 10(10) M(-1 )s(-1). Our work suggests that photochemical reactions may be a significant transformation pathway of SWCNTs in aquatic systems.

Sunlight-driven reduction of silver ions by natural organic matter: formation and transformation of silver nanoparticles.

Photobiogeochemical reactions involving metal species can be a source of naturally occurring nanoscale materials in the aquatic environment. This study demonstrates that, under simulated sunlight exposure, ionic Ag is photoreduced in river water or synthetic natural water samples that contain natural organic matter (NOM), forming Ag nanoparticles (AgNPs) that transform in size and shape and precipitate out upon extended irradiation. We show that the dissolved oxygen concentration does not appear to affect AgNP formation rates, indicating that reactive transients such as superoxide, hydrated electron, and triplet NOM do not play a large role. By varying pH and NOM concentrations and adding competing cations on the AgNP formation, we present three lines of evidence to show that Ag ion photoreduction likely involves ionic Ag binding to NOM. Our work suggests that photochemical reactions involving ionic Ag and NOM can be a source of nanosized Ag in the environment.