The co-existence of heavy metals and organic compounds including Cr(VI) and p-cresol (pC) in water environment becoming a challenge in the treatment processes. Herein, the synchronous photocatalytic reduction of Cr(VI) and oxidation of pC by silver oxide decorated on fibrous silica zirconia (AgO/FSZr) was reported. In this study, the catalysts were successfully developed using microemulsion and electrochemical techniques with various AgO loading (1, 5 and 10 wt%) and presented as 1, 5 and 10-AgO/FSZr. Catalytic activity was tested towards simultaneous photoredox of hexavalent chromium and p-cresol (Cr(VI)/pC) and was ranked as followed: 5-AgO/FSZr (96/78%) > 10-AgO/FSZr (87/61%) > 1-AgO/FSZr (47/24%) > FSZr (34/20%). The highest photocatalytic activity of 5-AgO/FSZr was established due to the strong interaction between FSZr and AgO and the lowest band gap energy, which resulted in less electron-hole recombination and further enhanced the photoredox activity. Cr(VI) ions act as a bridge between the positive charge of catalyst and cationic pC in pH 1 solution which can improve the photocatalytic reduction and oxidation of Cr(VI) and pC, respectively. The scavenger experiments further confirmed that the photogenerated electrons (e⁻) act as the main species for Cr(VI) to be reduced to Cr(III) while holes (h⁺) and hydroxyl radicals are domain for photooxidation of pC. The 5-AgO/FSZr was stable after 5 cycles of reaction, suggesting its potential for removal of Cr(VI) and pC simultaneously in the chemical industries.

Waste date palm-derived biochar (DPBC) was modified with nano-zerovalent iron (BC-ZVI) and silica (BC-SiO₂) through mechanochemical treatments and evaluated for arsenate (As(V)) removal from water. The feedstock and synthesized adsorbents were characterized through proximate, ultimate, and chemical analyses for structural, surface, and mineralogical compositions. BC-ZVI demonstrated the highest surface area and contents of C, N, and H. A pH range of 2–6 was optimum for BC-ZVI (100% removal), 3–6 for DPBC (89% removal), and 4–6 for BC-SiO₂ (18% removal). Co-occurring PO₄³⁻ and SO₄²⁻ ions showed up to 100% reduction, while NO₃⁻ and Cl⁻ ions resulted in up to 26% reduction in As(V) removal. Fitness of the Langmuir, Freundlich and Redlich-Peterson isotherms to As(V) adsorption data suggested that both mono- and multi-layer adsorption processes occurred. BC-ZVI showed superior performance by demonstrating the highest Langmuir maximum adsorption capacity (26.52 mg g⁻¹), followed by DPBC, BC-SiO₂, and commercial activated carbon (AC) (7.33, 5.22, and 3.28 mg g⁻¹, respectively). Blockage of pores with silica particles in BC-SiO₂ resulted in lower As(V) removal than that of DPBC. Pseudo-second-order kinetic model fitted well with the As(V) adsorption data (R² = 0.99), while the Elovich, intraparticle diffusion, and power function models showed a moderate fitness (R² = 0.53–0.93). The dynamics of As(V) adsorption onto the tested adsorbents exhibited the highest adsorption rates for BC-ZVI. As(V) adsorption onto the tested adsorbents was confirmed through post-adsorption FTIR, SEM-EDS, and XRD analyses. Adsorption of As(V) onto DPBC, BC-SiO₂, and AC followed electrostatic interactions, surface complexation, and intraparticle diffusion, whereas, these mechanisms were further abetted by the higher surface area, nano-sized structure, and redox reactions of BC-ZVI.

Because of the complexity of contaminants infiltrating groundwater, it is necessary to study the co-transport of contaminants in the vadose and saturated zones. To investigate the role of inorganic colloids in the transport of biocolloids through porous media, a series of experiments were performed using columns packed with sand. The Escherichia coli phage (E. coli phage) was used as the model virus and silica as the model colloid in this study. The model virus exhibited a higher degree of attachment when compared with silica under similar experimental conditions. Under unsaturated flow conditions, the degree of virus retention was higher than in the corresponding saturated flow case, regardless of the presence of silica. Mass recovery and breakthrough curve data showed that silica hindered virus transport in saturated porous media. The model virus exhibited a higher degree of retention in the presence of silica. This could be related to pore structure changes caused by aggregated virus-silica particles located within the pores of the sand. Conversely, the suspended virus retained at the air-water interface provided new retention sites for other colloids; the retention was observed to be higher in the presence of colloidal silica in the saturated columns. In the corresponding unsaturated experiments, silica was observed to play the opposite function with respect to virus transport, which demonstrated that silica facilitated virus transport in the presence of unsaturated porous media. Capillary forces were stronger than the virus-silica interactions, and inhibited the aggregation of particles. Suspended silica competes with the virus for sorption sites because of a high affinity for the air-water interface. This competition inhibits virus retention by electrostatic repulsion of like-charged particles, and concomitantly facilitates virus transport under unsaturated conditions.

Silica nanoparticles (SiNPs) can reduce both quality and quantity of sperm via inhibiting the progress of meiosis and mitosis and inducing apoptosis of spermatogenic cells, however, their specific mechanism and effects on the later stage of spermatogenesis are still unclear. To investigate the effects of SiNPs on the reproductive system, male mice were treated with SiNPs (0, 1.25, 5 and 20 mg/kg.bw) via intratracheal instillation once every 3 days and for a total of 15 days. Results revealed that exposure to SiNPs induced reduction in the rate of sperm activity, histological abnormalities in seminiferous epithelium as well as apoptosis of spermatogenic cells, which are associated with decreased level of Lethal (3) malignant brain tumor like 2 (L3MBTL2) and activation of DNA damage-p53-mitochondrial apoptosis pathways. Moreover, reduction in L3MBTL2 level caused by SiNPs also led to the lower expression of RNF8-ubH2A/ubH2B pathway, thus resulting in incomplete histone-to-protamine exchange. These results suggest that the inhibition of L3MBTL2 expression caused by SiNPs not only activates DNA damage-p53-mitochondrial apoptosis pathway leading to the apoptosis of spermatogenic cells, but also inhibits RNF8-ubH2A/ubH2B pathway resulting in incomplete histone-to-protamine exchange, thereby affected spermatogenesis. This indicates that L3MBTL2 plays an important role in reproductive toxicity of males caused by SiNPs.

Antifouling booster biocides are chemicals used in protective paints to tackle the adhesion of fouling organisms to maritime artificial structures. However, they are also known to exert toxic effects on non-target organisms. Recent research developments have highlighted the potential use of engineered micro/nanomaterials (EMNMs) as carriers of antifouling booster biocides in order to control their release and to reduce the harmful effects on living biota. In the present study, we sought to assess the toxicity of two commercially-available booster biocides: (zinc pyrithione (ZnPT) and copper pyrithione (CuPT)); three unloaded engineered micro/nanomaterials (EMNMs); layered double hydroxides (LDH), silica nanocapsules (SiNC), polyurea microcapsules (PU); , and six novel EMNMs (loaded with each of the two biocides). The exposure tests were conducted on the larval stage (nauplii) of the brine shrimp Artemia salina and on two embryonic developmental stages of the European purple sea urchin Paracentrotus lividus. The findings indicate that the unloaded LDH and PU (i.e. both biocide-free EMNMs) have non/low toxic effects on both species. The unloaded SiNC, in contrast, exerted a mild toxic effect on the A. salina nauplii and P. lividus embryos. The free biocides presented different toxicity values, with ZnPT being more toxic than CuPT in the P. lividus assays. LDH-based pyrithiones demonstrated lower toxicity compared to the free forms of the state-of-the-art compounds, and constitute good candidates in terms of their antifouling efficacy.

Stabilizing cadmium by incorporating it into crystalline products is an effective approach to detoxify cadmium-containing wastes. In this study, two Si-rich matrices in amorphous and crystalline forms (i.e., silica fume and α-quartz, respectively) were employed to incorporate Cd. The processing parameters, namely the type of Si-rich matrix, Cd/Si molar ratio (Г) and sintering temperature, were thoroughly investigated using quantitative X-ray diffraction technique. Cd incorporation was more energetically favored when silica fume was used rather than when α-quartz was used because of the lower Gibbs free energy of formation for silica fume. The sintering temperature and Г values substantially affected the formation of three cadmium silicates, namely monoclinic CdSiO₃, orthorhombic Cd₂SiO₄, and tetragonal Cd₃SiO₅. CdSiO₃ formed only in Г = 1.0 systems. Cd₂SiO₄ was dominant in all reactive systems. In Г = 3.0 systems, Cd₃SiO₅ rather than Cd₂SiO₄ was the predominant Cd-hosting product at temperatures above 850 °C. Leaching test results demonstrated that CdSiO₃ possessed the highest acid resistance among the cadmium silicates. The leachability of Cd₂SiO₄ was very similar to that of Cd₃SiO₅. CdSiO₃ preferred incongruent dissolution, whereas Cd₂SiO₄ and Cd₃SiO₅ favored near-congruent dissolution. This study delineated the feasibility of cadmium incorporation by Si-rich matrices, identifying a promising approach for cadmium detoxification.

An isotope-dilution ultra-performance liquid chromatography–electrospray tandem mass spectrometry method combined with dansylation was established to sensitively quantify four steroid estrogens (estrone, 17α-estradiol, 17β-estradiol and 17α-ethynylestradiol) and bisphenol A in sewage influent and effluent. A simple hexane extraction was performed from a small volume (10 mL), followed by dansyl chloride derivatization and purification with a silica cartridge. The method effectively reduced the matrix effects in sample extract and permitted the selective and sensitive determination of target compounds from complicated matrices. The detection limits of the method for steroid estrogens were 0.20–0.90 ng L⁻¹ in influent and 0.10–0.20 ng L⁻¹ in effluent samples. For bisphenol A, the limits detection of the method were 20 and 0.80 for influent and effluent samples, respectively. Recoveries of 85%–96% were observed in all matrices. The method was applied to analyze residual estrogens and bisphenol A in sewage influent and effluent samples from Beijing, China. The concentrations of bisphenol A (636–1200 ng L⁻¹) were up to 250 times higher than those of steroid estrogens. Estrone was the dominant estrogen in influent and effluent samples, while similar concentrations of 17α-estradiol and 17β-estradiol were detected in all samples.

Although it was recently determined that silicon can alleviate cadmium (Cd) toxicity in rice, the effects of silicon properties and the molecular mechanisms are still unclear. Here, the effect of silica nanoparticles (SiNPs) on Cd toxicity in rice was examined using cells cultured in suspension in the presence or absence of SiNPs (19 nm, 48 nm and 202 nm). The results showed that the presence of SiNPs substantially enhanced the proportion of live cells to 95.4%, 78.6% and 66.2%, respectively, suggesting that the extent of alleviation of Cd toxicity decreased gradually with size of SiNPs. The morphological results showed that dramatic damage and severe structural changes in the organelle integrity of cells occurred in the absence of SiNPs, whereas the cells exposed to the SiNPs remained nearly intact even in the presence of high concentrations of Cd. Furthermore, the SiNPs accumulated on the surface of the rice cells. Using inductively coupled plasma mass spectroscopy, Cd accumulated preferentially in plant cells with cell walls. In addition, noninvasive microtest technology showed that the average Cd2+ influx in those treated with SiNPs (19 nm, 48 nm and 202 nm) decreased by 15.7-, 11.1- and 4.6-fold, respectively. The gene expression of Cd uptake and transport (OsLCT1 and OsNramp5) was inhibited by SiNPs, but the gene expression of Cd transport into vacuole (OsHMA3) and Si uptake (OsLsi1) was enhanced by the SiNPs. These results indicate that the presence of SiNPs increased at least 1.87-fold the Si uptake capacity and inhibited the Cd uptake capacity, which together resulted in the alleviation of the toxicity of Cd in rice. This study provided a molecular-scale insight into the understanding of the SiNPs-induced alleviation of the toxicity of Cd in rice.

In this current work, the magnetic composite microsphere containing glutamine modified chitosan and silica coated Fe3O4 nanoparticles (CS-Gln-MCM) has been successfully prepared and extensively characterized, which is a kind of biodegradable materials. CS-Gln-MCM shows enhanced removal efficiency for both acid green 25 (AG25), an amphoteric dye, and mercury ions (Hg²⁺) from water in the respective while measured pH range compared with chitosan magnetic composite microsphere (CS-MCM) without modification. It is due to the fact that the grafted amino acid provides a variety of additional adsorption active sites and diverse adsorption mechanisms are involved. In AG25 and Hg²⁺ aqueous mixture, the modified adsorbents bear preferential adsorption for AG25 over Hg²⁺ in strong acidic solutions ascribed to multiple interactions between AG25 and CS-Gln-MCM, such as hydrogen bonding and electrostatic interactions. While, in weak acidic conditions, an efficient simultaneous removal is observed for different adsorption effects involved in aforementioned two pollutants. Besides, CS-Gln-MCM illuminates not only short equilibrium time for adsorption of each pollutant less than 20.0 min but also rapid magnetic separation from water and efficient regeneration after saturated adsorption. Therefore, CS-Gln-MCM bears great application potentials in water treatment.

Silica nanoparticles (SiO2 NPs) can cause health hazard after their release into the environment. Adsorption of natural organic matter and biomolecules on SiO2 NPs alters their surface properties and cytotoxicity. In this study, SiO2 NPs were treated by bovine serum albumin (BSA) and humic acid (HA) to study their effects on the integrity and fluidity of model cell membranes. Giant and small unilamellar vesicles (GUVs and SUVs) were prepared as model cell membranes in order to avoid the interference of cellular activities. The microscopic observation revealed that the BSA/HA treated (BSA-/HA-) SiO2 NPs took more time to disrupt membrane than untreated-SiO2 NPs, because BSA/HA adsorption covered the surface SiOH/SiO- groups and weakened the interaction between NPs and phospholipids. The deposition of SiO2 NPs on membrane was monitored by a quartz crystal microbalance with dissipation (QCM-D). Untreated- and HA-SiO2 NPs quickly disrupted the SUV layer on QCM-D sensor; BSA-SiO2 NPs attached on the membranes but only caused slow vesicle disruption. Untreated-, BSA- and HA-SiO2 NPs all caused the gelation of the positively-charged membrane, which was evaluated by the generalized polarity values. HA-SiO2 NPs caused most serious gelation, and BSA-SiO2 NPs caused the least. Our results demonstrate that the protein adsorption on SiO2 NPs decreases the NP-induced membrane damage.