Particulate matter (PM) can strongly affect redox biochemistry and therefore induce the response of the immune system and aggravate the course of autoimmune diseases. Nanoparticles containing transition metal compounds possessing semiconductor properties (TiO2, ZnO) may act as photocatalysts and accelerate the generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS). In this study, the NIST standard reference material, SRM 1648a, has been analyzed in terms of this consideration. Organic compounds present in SRM 1648a were removed by cold oxygen plasma treatment. Samples of SRM 1648a with removed organic content (<2% of organic carbon, <1% of nitrogen) were obtained within 2 h of this treatment. The treatment did not affect the morphology of the powder. The reference material and PM2.5 collected in Kraków are composed of smaller particles and nanoparticles forming aggregates. The efficiency of (photo)generation of hydroxyl radicals and singlet oxygen was compared for original and organics-free samples. The analyzed samples showed the highest activity towards ROS generation when exposed to UV-vis-NIR light, moderate under UV irradiation, and the lowest in dark. Data collected in the present study suggest that the organic fraction is mostly responsible for singlet oxygen generation, as almost twice higher efficiency of 1O2 generation was observed for the original NIST sample compared to the material without the organic fraction. However, particulate matter collected in Kraków was found to have a five times higher activity in singlet oxygen generation (compared for original NIST and Kraków dust samples).

A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO₂ nanoparticles and TiO₂/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO₂ and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO₂ and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

The effect of titanium dioxide nanoparticles (nano-TiO2) on the bioaccumulation and biotransformation of arsenic (As) remains largely unknown. In this study, we exposed two freshwater algae (Microcystis aeruginosa and Scenedesmus obliquus) to inorganic As (arsenite and arsenate) with the aim of increasing our understanding on As bioaccumulation and methylation in the presence of nano-TiO2. Direct evidence from transmission electron microscope (TEM) images show that nano-TiO2 (anatase) entered exposed algae. Thus, nano-TiO2 as carriers boosted As accumulation and methylation in these two algae species, which varied between inorganic As speciation and algae species. Specifically, nano-TiO2 could markedly enhance arsenate (As(V)) accumulation in M. aeruginosa and arsenite (As(III)) accumulation in S. obliquus. Similarly, we found evidence of higher As methylation activity in the M. aeruginosa of As(III) 2 mg L−1 nano-TiO2 treatment. Although this was also true for the S. obliquus (As(V)) treatment, this species exhibited higher As methylation compared to M. aeruginosa, being more sensitive to As associated with nano-TiO2 compared to M. aeruginosa. Due to changes in pH levels inside these exposed algae, As dissociation from nano-TiO2 inside algal cells enhanced As methylation. Accordingly, the potential influence of nanoparticles on the bioaccumulation and biotransformation of their co-contaminants deserves more attention.

Bisphenol A (BPA) is a widely concerned endocrine disrupting chemical and hard to be removed through conventional wastewater treatment processes. In this study, we developed a TiO2 decorated titanate nanotubes composite (TiO2/TNTs) and used for photocatalytic degradation of BPA. TEM and XRD analysis show that the TiO2/TNTs is a nano-composite of anatase and titanate, with anatase acting as the primary photocatalytic site and titanate as the skeleton. TiO2/TNTs exhibited excellent photocatalytic reactivity and its easy-settling property leaded to good reusability. After 5 reuse cycles, TiO2/TNTs also could photo-degrade 91.2% of BPA with a high rate constant (k1) of 0.039 min⁻¹, which was much better than TiO2 and TNTs. Higher pH facilitated photocatalysis due to more reactive oxygen species produced and less material aggregation. The presence of NaCl and CaCl2 showed negligible effects on BPA degradation, but NaHCO3 caused an inhibition effect resulting from consumption of ·OH. Humic acid inhibited degradation mainly due to blockage of the active sites of TiO2/TNTs. Degradation pathway was well interpreted through theoretical calculation. Hydroxyl radical played the dominate role in BPA photodegradation, and the atoms of BPA with high Fukui index based on density-functional theory (DFT) calculation are the radical easy-attacking (f⁰) sites. Considering the good photocatalytic reactivity, reusability, stability and settle property, TiO2/TNTs promises to be an efficient alternative for removal of organic compounds from wastewaters.

The mechanism of enhanced accumulation of organic contaminants in crops with engineered nanomaterials (ENMs) were investigated by co-exposure of crops (Ipomoea aquatica Forsk (Swamp morning-glory), Cucumis sativus L. (cucumber), Zea mays L. (corn), Spinacia oleracea L. (spinach) and Cucurbita moschata (pumpkin))to a range of chemicals (polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polybrominated diphenyl ether (PBDE)) and ENMs (TiO2, Ag, Al2O3, graphene, carbon nanotubes (CNTs)) in soil. Induced by 50 mg kg−1 graphene co-exposure, the increase range of BDE-209, BaP, p,p′-DDE, HCB, PYR, FLU, ANT, and PHEN in the plants were increased in the range of 7.51–36.42, 5.69–32.77, 7.09–59.43, 11.61–66.73, 4.58–57.71, 5.79–109.07, 12.85–109.76, and15.57–127.75 ng g−1, respectively. The contaminants in ENMs-spiked and control soils were separated into bioavailable, bound and residual fractions using a sequential ultrasonic extraction procedure (SUEP) to investigate the mechanism of the enhanced accumulation. The bioavailable fraction in spiked soils showed no significant difference (p > 0.05) from that in the control, while the bound fraction increased in equal proportion (p > 0.05) to the reduction in the residual fraction. These results implied that ENMs can competitively adsorbed the bound of organic contaminants from soil and co-transferred into crops, followed by a portion of the residual fraction transferred to the bound fraction to maintain the balance of different fractions in soils. The mass balance was all higher than 98.5%, indicating the portion of degraded contaminants was less than 1.5%. These findings could expand our knowledge about the organic contaminants accumulation enhancement in crops with ENMs.

Nanosized particles (NPs), such as TiO₂, Silver, graphene NPs, nanoscale zero-valent iron, carbon nanotubes, etc., are increasingly used in industrial processes, and releases at production plants and from landfills are likely scenarios for the next years. As a consequence, appropriate procedures and tools to quantify the risks for human health associated to these releases are needed.The tiered approach of the standard ASTM procedure (ASTM-E2081-00) is today the most applied for human health risk assessment at sites contaminated by chemical substances, but it cannot be directly applied to nanoparticles: NP transport along migration pathways follows mechanisms significantly different from those of chemicals; moreover, also toxicity indicators (namely, reference dose and slope factor) are NP-specific. In this work a risk assessment approach modified for NPs is proposed, with a specific application at Tier 2 to migration in groundwater. The standard ASTM equations are modified to include NP-specific transport mechanisms. NPs in natural environments are typically characterized by a heterogeneous set of NPs having different size, shape, coating, etc. (all properties having a significant impact on both mobility and toxicity). To take into account this heterogeneity, the proposed approach divides the NP population into classes, each having specific transport and toxicity properties, and simulates them as independent species. The approach is finally applied to a test case simulating the release of heterogeneous Silver NPs from a landfill. The results show that taking into account the size-dependent mobility of the particles provides a more accurate result compared to the direct application of the standard ASTM procedure. In particular, the latter tends to underestimate the overall toxic risk associated to the nP release.

Gut microbiota is of critical relevance to host health. However, toxicological understanding of environmental pollutants on gut microbiota is limited, not to mention their combined effects. In the present study, adult zebrafish (Danio rerio) were exposed to titanium dioxide nanoparticles (nano-TiO₂; 100 μg/L), bisphenol A (BPA; 0, 2, and 20 μg/L) or their binary mixtures for three months. Sequencing of 16S rRNA amplicons found that nano-TiO₂ and BPA coexposure shifted the intestinal microbial community, interacting in an antagonistic manner when the BPA concentration was low but in a synergistic manner at a higher BPA concentration. Sex- and concentration-dependent responses to the coexposure regime were also observed for zebrafish growth and intestinal health (e.g. neurotransmission, epithelial barrier permeability, inflammation, and oxidative stress). Correlation analysis showed that oxidative stress after nano-TiO₂ and BPA coexposure was tightly associated with the imbalanced ratio of pathogenic Lawsonia and normal metabolic Hyphomicrobium, where higher abundance of Lawsonia but lower abundance of Hyphomicrobium were induced concurrently. A positive relationship was observed between zebrafish body weight and the abundance of Bacteroides in the gut, which was also closely associated with the genera of Anaerococcus, Finegoldia, and Peptoniphilus. This study revealed, for the first time, the combined effects of nano-TiO₂ and BPA coexposure on the dynamics of the gut microbiome, which proved to have toxicological implications for zebrafish host health.

In situ photocatalytic degradation of dissolved organic matter (DOM) of stormwater runoff can efficiently improve the aquatic environment quality and relieve the wastewater treatment pressure. In this work, photocatalytic degradation of DOM in TiO₂ (AEROXIDE® P-25) photocatalyst under illumination of ultraviolet (UV) light was carried out, considering the influence of various factors like TiO₂ dosage, solution pH along with the existence of co-existing ions (Cu²⁺ and H₂PO₄⁻). Generally, the variations of dissolved organic carbon (DOC), UV-based parameters and peak intensities of fluorescent constituents with UV exposure time fitted perfectly with the pseudo-first-order kinetics model. The total DOM removal efficiency was affected by diversiform factors like adsorption capacity of TiO₂, UV light utilization efficiency, reactive free radicals produced and the influence of co-existing ions. The results of fluorescence excitation-emission matrix (EEM) coupled with parallel factor analysis (PARAFAC) modeling demonstrated that all the photodegradation rates for three identified fluorescent constituents (protein-like constituent 1 and 3, humic-like constituent 2) were faster than UV-absorbing chromophores, suggesting the DOM molecules in urban stormwater runoff contained much more π*-π transition structures. In addition, H₂PO₄⁻ ions affected the photodegradation of DOM by capturing positive holes (h⁺) and hydroxyl radical (·OH), whereas Cu²⁺ ions were inclined to generate Cu-protein complexes that were more difficult to degrade than the other Cu-DOM complexes. This study supplied novel insights into the photocatalytic degradation mechanism of individual organic constituent in urban stormwater runoff and explored the influences of co-existing contaminants on their adsorption-photocatalysis processes.

In this work we have investigated in details the process of degradation of the 4-amino-6-chlorobenzene-1,3-disulfonamide (ABSA), stable hydrolysis product of frequently used pharmaceutical hydrochlorothiazide (HCTZ), as one of the most ubiquitous contaminants in the sewage water. The study encompassed investigation of degradation by hydrolysis, photolysis, and photocatalysis employing commercially available TiO₂ Degussa P25 catalyst. The process of direct photolysis and photocatalytic degradation were investigated under different type of lights. Detailed insights into the reactive properties of HCTZ and ABSA have been obtained by density functional theory calculations and molecular dynamics simulations. Specifically, preference of HCTZ towards hydrolysis was confirmed experimentally and explained using computational study. Results obtained in this study indicate very limited efficiency of hydrolytic and photolytic degradation in the case of ABSA, while photocatalytic degradation demonstrated great potential. Namely, after 240 min of photocatalytic degradation, 65% of ABSA was mineralizated in water/TiO₂ suspension under SSI, while the nitrogen was predominantly present as NH4+. Reaction intermediates were studied and a number of them were detected using LC-ESI-MS/MS. This study also involves toxicity assessment of HCTZ, ABSA, and their mixtures formed during the degradation processes towards mammalian cell lines (rat hepatoma, H-4-II-E, human colon adenocarcinoma, HT-29, and human fetal lung, MRC-5). Toxicity assessments showed that intermediates formed during the process of photocatalysis exerted only mild cell growth effects in selected cell lines, while direct photolysis did not affect cell growth.

The (un)intentional release of titanium dioxide nanoparticles (TiO₂ NPs) poses potential risks to the environment and human health. Phosphorus (P) and humic acid (HA) usually coexist in the natural environments. This study aims at investigating the transport and retention behaviors of TiO₂ NPs in the single and binary systems of P and HA in water-saturated porous media. The experimental results showed that HA alone favored the transport of TiO₂ NPs in sand columns to a greater extent than that of P alone at pH 6.0. Interestingly, the co-presence of P and HA acting in a synergistic fashion enhanced the transport of TiO₂ NPs in sand-packed columns more significantly compared to that in the single-presence of P or HA. Particularly, P plays a dominant role in the synergistic effect. This is largely due to the competitive effect between P and HA for the same adsorption sites on the sand surfaces favorable for TiO₂ NPs retention. A two-site kinetic attachment model that considers Langmuirian blocking of particles at one site provided a good approximation of TiO₂ NPs transport. Modeled first-order attachment coefficient (k₂) and the maximum solid-phase retention capacity on site 2 (Sₘₐₓ₂) for P or HA alone were larger than those in the co-presence of P and HA, suggesting a less retention degree of TiO₂ NPs in the binary system of P and HA. Our findings indicate that the mobility of TiO₂ NPs is expected to be appreciable in soil and water environments, where P and HA are rich and always co-present at low pH conditions.