This paper investigated the application of graphite particle electrodes to the removal of Zn, Pb, Cu, and Cd from municipal solid waste incineration (MSWI) fly ashes in a three-dimensional (3D) electrokinetic reactor. The influences of the voltage gradient, mass ratio of graphite powers to fly ashes, nitric acid concentrations, proposing times, and liquid-solid (L-M) ratios on the remedial efficiencies of MSWI fly ashes were comprehensively studied in an orthogonal deign and a sequential double-factor setup. Significant analysis showed that changes in the mass ratios and nitric acid concentrations both had a statistically significant effect on the removals of Zn and Pb. Proposing times and L-M ratios both remarkably affected the removals of heavy metals (HMs) in a 3D electrochemical system. The graphite powers had a narrower distribution interval and slightly larger surface areas compared with MSWI fly ashes, which relented pH gradients over the time in the electrochemical experiments and minimized the bubble barricade caused by the hydrolysis. The particle electrode had increased the residue factions of Zn, Pb, Cu, and Cd in S1 region by approximately 216%, 136%, 309%, and 950%, respectively, compared with the raw MSWI fly ashes. The addition of graphite powders to a two-dimensional (2D) electrochemical process strengthened hydrolysis reactions, shortened time for the redistribution of pH balance, decreased the tortuosity of migration path, and increased the desorption concentrations of HMs in the sample area.

The multiple effect of pristine graphene (pG) toxicity on cardiovascular developmental defects was assessed using zebrafish as a model. Recently, the nanotoxicity is emerging as a critical issue, and it is more significant in embryogenesis. Especially, graphene and its derivatives have attracted a lot of interest in biomedical applications. However, very little is known about the toxic effects of pG which has been widely used carbon nanomaterial according to concentration and its effects on biological and cardiovascular development. In the present study, we examined the development of zebrafish embryos by exposing to pG (5, 10, 15, 20 and 25 μg/L) under different developmental toxicity end-points such as cardiotoxicity, cardiovascular defect, retardation of cardiac looping, apoptosis and globin expression analysis. For this, the developmental cardiotoxicity of pG at different concentrations and the specific cardiovascular defects thereof were elucidated for the first time. As a result, the exposure to pG was found to be a potential risk factor to cardiovascular system of zebrafish embryos. However, a further study on the variations of physical, molecular properties and mechanisms of nanotoxicity which vary depending on production method and surface functionalization is required. In addition, the potential risks of pG flakes to aquatic organisms and human health should be considered or checked before releasing them to the environment.

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.

The implications of humic acid (HA) regarding surface properties of graphene materials and their interactions with phthalic acid esters (PAEs) are not vivid. We report the role of HA on graphene oxide (GO) and reduced graphene oxide (RGO) for sorption-desorption behavior of PAEs. Besides higher surface area and pore volume, the hydrophobic π-conjugated carbon atoms on RGO ensured prominent adsorption capacity towards PAEs in comparison to hydrophilic GO, highlighting the hydrophobic effect. After adjusting for the hydrophobic effect by calculating the hexadecane-water partition coefficient (KHW) normalized adsorption coefficient (Kd/KHW), the dimethyl phthalate (DMP) molecule portrayed a higher adsorption affinity towards RGO by π-π electron donor–acceptor (EDA) interaction for active sites on graphene interface via sieving effect. In contrast to RGO, the weak π-π EDA interactions and H-bonding was observed between the carbonyl groups of PAEs and oxygen containing functional groups on GO. There was no obvious change in morphologies of GO and RGO before and desorption as revealed by SEM and TEM images, as desorption hysteresis did not occur in all conditions. The presence of HA also resulted in shielding effect thereby decreasing the adsorption rate and capacity of diethyl phthalate (DEP) on GO and RGO, while it had little effect on DMP, probably due to the adsorbed HA as new active sites. The desorption of DMP and DEP on RGO in presence of HA was quick and enhanced. These results should be important for evaluating the fate and health risk of graphene materials and PAEs in the environment.

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.

The cleaning-up of viscous oil spilled in ocean is a global challenge, especially in Bohai, due to its slow current movement and poor self-purification capacity. Frequent oil-spill accidents not only cause severe and long-term damages to marine ecosystems, but also lead to a great loss of valuable resources. To eliminate the environmental pollution of oil spills, an efficient and environment-friendly oil-recovery approach is necessary. In this study,¹expanded graphite (EG) modified by CTAB-KBr/H₃PO₄ was synthesized via composite intercalation agents of CTAB-KBr and natural flake graphite, followed by the activation of phosphoric acid at low temperature. The resultant modified expanded graphite (M-EG) obtained an interconnected and continuous open microstructure with lower polarity surface, more and larger pores, and increased surface hydrophobicity. Due to these characteristics, M-EG exhibited a superior adsorption capacity towards marine oil. The saturated adsorption capacities of M-EG were as large as 7.44 g/g for engine oil, 6.12 g/g for crude oil, 5.34 g/g for diesel oil and 4.10 g/g for gasoline oil in 120min, exceeding the capacity of pristine EG. Furthermore, M-EG maintained good removal efficiency under different adsorption conditions, such as temperature, oil types, and sodium salt concentration. In addition, oils sorbed into M-EG could be recovered either by a simple compression or filtration-drying treatment with a recovery ratio of 58–83%. However, filtration-drying treatment shows better performance in preserving microstructures of M-EG, which ensures the adsorbents can be recycled several times. High removal capability, fast adsorption efficiency, excellent stability and good recycling performance make M-EG an ideal candidate for treating marine oil pollution in practical application.

To further assess the human being's exposure to polycyclic aromatic hydrocarbons (PAHs) through the dietary pathway, understanding the partitioning of these chemicals co-existed with nanomaterials in edible vegetable systems deserves specific consideration. In this study, the fiber-optic fluorimetry was applied to in situ examine the effects of graphene (GNS) and graphene oxide (GO) nanosheets on the quantification and depuration of three-ringed phenanthrene (Phe) and four-ringed fluoranthene (Fla) adsorbed individually onto the living spinach (Spinacia oleracea L.) surfaces. When the GNS and GO dosages separately increased to the maximum values: a respective red-shift of 4–5 nm and blue-shift of 2–3 nm occurred for the optimal detection emission wavelengths (λem) of the two PAHs, indicating that individual GNS and GO resulted in different changes to the epicuticular wax (ECW) polarity; GNS-inducing fluorescence quenching for the PAHs was about two times greater than GO, owing to the stronger π-π interactions between PAH molecules and GNS relative to GO; the volatilization coefficients (kC1) were reduced by 31.1% versus 26.7% for Phe, and 51.6% versus 34.4% for Fla, mainly via providing an additional adsorbent and promoting the accessibility of the leaf cuticle; respective photolysis coefficients (kP2) of Phe and Fla decreased by 42.9% and 50.0% with GNS, primarily owing to the enhancement of the ECW light-adsorption capacity, but increased by 33.3% and 40.0% with GO due to its photocatalytic activities; overall, total depuration coefficients (kT1, kT2) of the two PAHs decreased by 11.1–55.6%. These findings demonstrate that GNS and GO significantly alter the depuration behavior of PAHs in vegetable systems, potentially posing a threat to the safety of edible vegetables.

Understanding of the interaction of graphene with natural polysaccharides (e.g., alginate) is crucial to elucidate its environmental fate. We investigated the impact of alginate on the agglomeration and stability of ¹⁴C-labeled few-layer graphene (FLG) in varying concentrations of monovalent (NaCl) and divalent (CaCl₂) electrolytes. Enhanced agglomeration occurred at high CaCl₂ concentrations (≥5 mM) due to the alginate gel networks formation in the presence of Ca²⁺. FLG enmeshed within extended alginate gel networks was observed under transmission electron microscope and atomic force microscope. However, background Na⁺ competition for binding sites with Ca²⁺ at the alginate surfaces shielded the gelation of alginate. FLG was readily dispersed by alginate under environmentally relevant ionic strength conditions (i.e., <200 mM Na⁺ and <5 mM Ca²⁺). In comparison with the bare FLG, the slow sedimentation of the alginate-stabilized FLG (158 μg/L) caused continuous exposure of this nanomaterial to freshwater snails, which ingested 1.9 times more FLG through filter-feeding within 72 h. Moreover, surface modification of FLG by alginate significantly increased the whole-body and intestinal levels of FLG, but reduced the internalization of FLG to the intestinal epithelial cells. These findings indicate that alginate will act as a stabilizing agent controlling the transport of FLG in aqueous systems. This study also provides the first evidence that interaction of graphene with natural polysaccharides affected the uptake of FLG in the snails, which may alter the fate of FLG in aquatic environments.

Crumpled graphene oxide nanosheets have drawn large attentions due to its compressibility and self-avoiding stacking as flat graphene sheets trend to aggregate and restack. Up to now, most of the synthesis approaches were relied on external substrates, such as elastic substrates or ultrasonic atomizer, and the crumpled structures were obtained in a solid state directly. Here we report a facile method to produce crumpled dispersive nanosheets in solution through general base-washing treatment by taking advantage of the amphipathy of GO nanosheets. With the dissociation of oxygen-functional groups on nanosheets in alkaline environment, highly water-soluble oxidative debris (OD) would fall off from the nanosheets due to the increase of electrostatic repulsions, and resulted in the crumple of the flat sheets, while the covalent oxygen-functional groups on the nanosheets were reserved. As a result, the nanosheets remained dispersible in solution, and could be used directly for surface modifications. Pt nanoparticles could be directly deposited onto both sides of the sheets through common nucleation and growth from precursor ions process. Compared with flat graphene-based hybrid, the catalytic performance of crumpled-graphene-Pt (CG-Pt) is more excellent and attractive, and corresponding apparent kinetic rate constant (kₐₚₚ) of CG-Pt toward 4-nitrophenol reduction is enhanced by 2.7–4.6-fold. This study provides a new and facile way to fabricate crumpled nanosheets and demonstrates to be easy modified for various purpose.

To investigate the chronic toxicity of graphene oxide (GO) and its functionalized products (GO-carboxyl, GO-imidazole and GO-polyethylene glycol), a two-generation study was conducted using the aquatic model species Daphnia magna. Each generation of daphnids were exposed for 21 days to 1.0 mg L−1 graphene material, with body length, neonate number, time of first brood and the intrinsic rate of natural increase (r) assessed as endpoints. Chronic exposure to GO, GO-carboxyl, and GO-imidazole had no adverse effect on body length or offspring number in the daphnid F0 generation, however, this exposure paradigm led to significant growth or reproduction inhibition in the following generation. Meanwhile, GO was found to show the strongest inhibitory effect, sequentially followed by GO-carboxyl and GO-imidazole. With exposure to GO-polyethylene glycol, no significant effects on growth or reproduction were observed for both F0 and F1 generation daphnids. These results reveal that carboxyl, imidazole and polyethylene glycol functional attachments alleviate the bio-toxicity of GO, especially polyethylene glycol. The increased C/O atomic ratio present in GO-carboxyl, GO-imidazole and GO-polyethylene glycol due to functionalization may mainly explain the reduced toxicity.