We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L−1) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L−1) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L−1) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

Graphene oxide (GO) and reduced graphene oxide (RGO) materials contain a variety of surface O-functional groups that are chemically reactive. When released into the environment these materials may significantly affect the abiotic transformation of organic contaminants, and therefore, may alter their fate and risks. We found that two GO and five RGO materials that varied in C/O ratio, hydrophobicity, and type/distribution of surface O-functionality all had catalytic effects on the dehydrochlorination of 1,1,2,2-tetrachloroethane (TeCA). Even though the catalytic effects of the materials originated from their deprotonated surface O-functional groups, which served as conjugated bases to catalyze the reaction, the catalytic efficiencies of the materials did not correlate strongly with their surface O contents. The spectroscopic evidence (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy), surface charge data, and adsorption experiments demonstrated that the catalytic efficiencies of the GO/RGO materials were controlled by a complex interplay of the type and distribution of surface O-functionality, as well as adsorption affinity of the materials. Both Ca2+ and Mg2+ inhibited the catalytic efficiency of the materials by binding to the surface O-functional groups, and consequently, decreasing the basicity of the functional groups. At an environmentally relevant concentration of 10 mg/L, Suwannee River humic acid (used as a model dissolved organic matter) alone had little effect on the dehydrochlorination of TeCA. However, it could inhibit the catalytic efficiency of the GO/RGO materials by coating on their surface and thus, decreasing the adsorption affinity of these materials for TeCA. The findings further underline the potentially important impacts of nanomaterials on contaminant fate and effects in the environment.

A novel PbO2/graphite felt electrode was constructed by electrochemical deposition of PbO2 on graphite felt and characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) analysis. The prepared electrode is a viable technology for inactivation of Escherichia coli, Enterococcus faecalis, and Artemia salina as indicator organisms in simulated ballast water treatment, which meets the International Maritime Organization (IMO) Regulation D-2. The effects of contact time and current density on inactivation were investigated. An increase in current density generally had a beneficial effect on the inactivation of the three species. E.faecalis and A.salina were more resistant to electrochemical disinfection than E. coli. The complete disinfection of E.coli was achieved in <8min at an applied current density of 253A/m2. Complete inactivation of E. faecalis and A.salina was achieved at the same current density after 60 and 40min of contact time, respectively. A. salina inactivation follows first-order kinetics.

TiO₂-graphene (TiO₂-GR) composites were successfully prepared by a two-step solvothermal method using titanium dioxide and natural graphite powder. X-ray diffraction (XRD) patterns showed that graphene oxide (GO) was prepared from natural flake graphite by a modified hydrothermal pressurized oxidation method. The results of Fourier transform infrared spectroscopy (FTIR) proved that TiO₂-GR composites were synthesized during the process of hydrothermal reaction while GO was changed into graphene. X-ray photoelectron spectroscopy (XPS) demonstrated that TiO₂ particles contacted closely with graphene via Ti–O–C bonds. The results of Raman spectra confirmed the existence of graphene in the TiO₂-GR composite. Scanning electron microscopy (SEM) images showed that TiO₂ particles were oval and grafted on the graphene sheet which was smooth with ripples. UV-visible diffuse reflectance spectra demonstrated that there was a red shift in the absorption edge of TiO₂-GR composite. The experimental results indicated that the TiO₂-GR composite had significantly adsorption-photocatalytic activity for the degradation of methylene blue (MB) dyes. The adsorption capacity (q ₘₐₓ) of TiO₂-6%GR-4h for MB was 41.32 mg ⋅ g⁻ ¹ calculated based on the Langmuir adsorption model, which was about 3.3 times the adsorption capacity of TiO₂. Adsorption kinetics studies showed that the adsorption process fit well with the pseudo-second-order model. It proved that the TiO₂-GR composites were more efficient than the pure TiO₂ in the field of environmental protection.

Bisphenol S (BPS), a new bisphenol analog, is considered to be a potential replacement for bisphenol A (BPA), which has gained concern because of its potentially adverse health impacts. Therefore, studies are needed to investigate the environmental fate and risks of this compound. In this study, the adsorption of BPS and four structural analogs on multi-walled carbon nanotubes (MWCNTs) and graphite (GP) were investigated. When solid-phase concentrations were normalized by the surface areas, oxygen-containing functional groups on the absorbents showed a positive impact on phenol sorption but inhibited the sorption of chemicals with two benzene rings. Among BPS analogs, diphenyl sulfone showed the lowest sorption when hydrophobic effects were ruled out. Chemicals with a butterfly structure, formed between the two benzene rings, showed consistently high sorption on MWCNTs, independent of the substituted electron-donating or accepting functional groups. This study emphasizes the importance of chemical conformation on organic, contaminant sorption on engineered, carbonaceous materials.

A heterogeneous Fenton catalyst Ce⁰–Fe⁰-reduced graphene oxide (Ce–Fe–RGO) was synthesized with chemical reduction methods and used for degradation of sulfamethazine. The introduction of Ce and graphene increased the dispersibility of iron particles which was confirmed by SEM and TEM. The results of VSM analysis showed good magnetism of Ce–Fe–RGO. The catalyst performance was compared with other kinds of catalysts (Fe⁰ and Ce⁰–Fe⁰) for degradation of sulfamethazine. The results showed that Ce⁰–Fe–RGO had good catalytic performance and adsorption. X-ray diffraction showed the change of iron oxide on catalyst surface after use. The total sulfur (TS), total nitrogen (TN), total organic carbon (TOC), and intermediates, such as small organic molecular and anion ions, were analyzed by IC under different pH conditions. Finally, the possible catalytic mechanism was tentatively proposed based on inhibitor experimental results and XPS characterization. The main active species was hydroxyl radical on catalyst surface and the transition between Ce³⁺ and Ce⁴⁺ which enhanced the reduction from Fe³⁺ to Fe²⁺ and formation of ·OH and ·O₂ ⁻.

The feasibility of using biochar as a sorbent to remove nine halogenated phenols (2,4-dichlorophenol, 2,4-dibromophenol, 2,4-difluorophenol, 2-chlorophenol, 4-chlorophenol, 2-bromophenol, 4-bromophenol, 2-fluorophenol, and 4-fluorophenol) and two pharmaceuticals (triclosan and ibuprofen) from water was examined through a series of batch experiments. Types of biochar, synthesized using various biomasses including fallen leaves, rice straw, corn stalk, used coffee grounds, and biosolids, were evaluated. Compared to granular activated carbon (GAC), most of the biochar samples did not effectively remove halogenated phenols or pharmaceuticals from water. The increase in pH and deprotonation of phenols in biochar systems may be responsible for its ineffectiveness at this task. When pH was maintained at 4 or 7, the sorption capacity of biochar was markedly increased. Considering maximum sorption capacity and properties of sorbents and sorbates, it appears that the sorption capacity of biochar for halogenated phenols is related to the surface area and carbon content of the biochar and the hydrophobicity of halogenated phenols. In the cases of triclosan and ibuprofen, the sorptive capacities of GAC, graphite, and biochars were also significantly affected by pH, according to the point of zero charge (PZC) of sorbents and deprotonation of the pharmaceuticals. Pyrolysis temperature did not affect the sorption capacity of halogenated phenols or pharmaceuticals. Based on the experimental observations, some biochars are good candidates for removal of halogenated phenols, triclosan, and ibuprofen from water and soil.

A large amount of soils are contaminated by leakage of polychlorinated biphenyls (PCBs) from sealed-up PCB-containing electrical equipment in China. Thermal dechlorination of soils contaminated with PCBs at a level of 108 mg g⁻¹ and PCB77 (3,3′,4,4′-tetrachlorobiphenyl) as a model isomer in conjunction with calcium oxide was investigated in this study. The PCB dechlorination rate improved with increased temperature and time. The highest dechlorination rate was 85.3 %, and temperature was the main influencing factor. Pentachlorobiphenyl and tetrachlorobiphenyl in soils decreased or disappeared in response to treatment at 350 and 400 °C for 4 h, while monochlorinated biphenyl and biphenyl were detected after the reaction, indicating the presence of a dechlorination/hydrogenation pathway. Discrepancy in chlorine balance was observed after low-temperature thermal dechlorination. The species of dechlorination products were identified as amorphous carbon containing a crystalline graphite plane structure and a carbonyl group-containing polymerized product, demonstrating the existence of a dechlorination/polymerization pathway. The yield of amorphous carbon and high-molecular-weight intermediates increased with heating time. The results showed that the discrepancy in chlorine balance was because of the generation of polymerized products and undetected intermediates.

In this study, separation and concentration of fatty acids (FA) from the synthetic food processing wastewater containing low concentration of FA (250 mg/L) were investigated using expanded graphite (EG) as a novel adsorbent at different temperatures (298~318 K). The adsorption results were further analyzed to verify adsorption mechanisms and thermodynamics of FA onto EG. Results show that the adsorption of FA onto EG was explained well by the Langmuir model with the maximum adsorption capacity up to 8.01 g FA/g EG at 298 K, and considerably affected by temperature. The adsorption kinetics fitted with pseudo-second-order kinetic model and the adsorption mechanism analysis showed that the intraparticle diffusion was not the rate-limiting step, but the coalescence of FA droplets played the significant role for novel adsorption of FA onto EG. The calculated activation energy and thermodynamic parameters such as Gibbs free energy change (ΔG⁰), enthalpy change (ΔH⁰), and entropy change (ΔS⁰) indicated that the adsorption of FA onto EG was very feasible, was highly spontaneous, occurred physically, was exothermic in nature, and was stable in aquatic environmental changes. Overall, FA can be effectively harvested and concentrated from the food processing wastewater by EG even at low concentration.

In the present work, the toxicity of three forms of graphene: pristine graphene (pG), graphene oxide (GO), and reduced graphene oxide (rGO) was investigated using a chicken embryo model. Fertilized chicken eggs were divided into the control group and groups administered with pG, GO, and rGO, in concentrations of 50, 500, and 5000 μg/ml. The experimental solutions were injected in ovo into the eggs, and at day 18 of incubation, the embryo survival, body and organ weights, the ultrastructure of liver samples, and the concentration of 8-hydroxy-2′-deoxyguanosine (8-OHdG) in the livers were measured. Survival of embryos decreased significantly after treatment with all types of graphene, but not in a dose-dependent manner. The body weights were only slightly affected by the highest doses of graphene, while the organ weights were not different among treatment groups. In all experimental groups, atypical hepatocyte ultrastructure and mitochondrial damage were observed. The concentration of the marker of DNA damage 8-OHdG in the liver significantly decreased after pG and rGO treatments. Further in vivo studies with different animal models are necessary to clarify the level of toxicity of different types of graphene and to estimate the concentrations appropriate to evaluate their biomedical applications and environmental hazard.