Microplastic (MP) pollution is an emerging issue in aquatic sciences. Little comparative information currently exists about the problem in coastal systems exposed to different levels of human impact. Here we report a year-long study on the abundance of MP in the water column of three estuaries on the east-coast of Australia. The estuaries are subject to different scales of human impact; the Clyde estuary has little human modification, the Bega estuary has a small township and single wastewater treatment works discharging to its waters, and the Hunter estuary which has multiple townships, multiple wastewater treatment plants, and heavy industry. MP abundance followed an expected pattern with the lowest abundance in the low-impact Clyde estuary (98 part. m³), moderate levels of MP in the moderately impacted Bega estuary (246 part. m³), and high MP abundance in the highly impacted Hunter estuary (1032 part. m³). The majority of particles were <200 μm and fragment-like rather than fiber-like. MP abundance was positively related to maximum antecedent rainfall in the Bega estuary, however there are no clear environmental factors that could explain MP variation in the other systems. MP were generally higher in summer and following freshwater inflow events. On the Hunter estuary MP abundance was at times as high as zooplankton abundance, and within the range of numbers reported in other highly impacted systems globally. The results confirm that higher levels of human impact lead to greater plastic pollution and highlight the need to examine aquatic ecosystems under a range of conditions in order to adequately characterize the extent of MP pollution in rivers and coastal systems.

Efficient containment and capture of uranium (U(VI)) from aqueous solution is an essential component to ensure socially and environmentally sustainable development. Herein, the three-dimensional graphene/titanium dioxide composite (3D GA/TiO₂) was synthesized and applied as an effective adsorbent to remove U(VI) from wastewater as a function of contact time, temperature, pH and ion strength. The 3D GA/TiO₂ material was characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The batch experiments results indicated that the adsorption of U(VI) on materials were fitted with the pseudo-second order kinetics and Langmuir models. More specifically, 3D GA/TiO₂ (441.3 mg/g) was observed to outperform the GO (280.0 mg/g), rGO (140.9 mg/g) and TiO₂ (98.5 mg/g) at pH 5.0, which was attributable to the excellent cooperative effects. Furthermore, XPS analyses and DFT calculations confirmed the formation of surface complexes between oxygen-containing group and U(VI) with the U–O bonds length of 2.348 Å (U–O1) and 2.638 Å (U–O2). Meanwhile, the adsorption energy was calculated to be 1.60 eV, which showed a very strong chemisorption during the interaction process. It is believed that the 3D GA/TiO₂ revealed good removal performance for uranyl ions, which showed a great potential application to control the nuclear industrial pollution.

The Athabasca Oil Sands Region (AOSR) in Alberta, Canada, is an important source of atmospheric pollutants, such as aerosols, that have repercussions on both the climate and human health. We show that the mean freezing temperature of snow-borne particles from AOSR was elevated (−7.1 ± 1.8 °C), higher than mineral dust which freezes at ∼ −15 °C and is recognized as one of the most relevant ice nuclei globally. Ice nucleation of nanosized snow samples indicated an elevated freezing ability (−11.6 ± 2.0 °C), which was statistically much higher than snow-borne particles from downtown Montreal. AOSR snow had a higher concentration (∼2 orders of magnitude) of >100 nm particles than Montreal. Triple quadrupole ICP-(QQQ)-MS/MS analysis of AOSR and Montreal snow demonstrated that most concentrations of metals, including those identified as emerging nanoparticulate contaminants, were much more elevated in AOSR in contrast to Montreal: 34.1, 34.1, 16.6, 5.8, 0.3, 0.1, and 9.4 mg/m³ for Cr, Ni, Cu, As, Se, Cd, and Pb respectively, in AOSR and 1.3, 0.3, 2.0, <0.03, 0.1, 0.03, and 1.2 mg/m³ in Montreal snow. High-resolution Scanning Transmission Electron Microscopy/Energy-dispersive X-ray Spectroscopy (STEM-EDS) imaging provided evidence for various anthropogenic nano-materials, including carbon nanotubes resembling structures, in AOSR snow up to 7–25 km away from major oil sands upgrading facilities. In summary, particles characterized as coming from oil sands are more efficient at ice nucleation. We discuss the potential impacts of AOSR emissions on atmospheric and microphysical processes (ice nucleation and precipitation) both locally and regionally.

Metal pollution has been associated with anthropogenic activities, such as effluents and emissions from mines. Soil could be exposure route of wild rats to metals, especially in mining areas. The aim of this study was to verify whether soil exposure under environmentally relevant circumstances results in metal accumulation and epigenetic modifications. Wistar rats were divided to three groups: 1) control without soil exposure, 2) low-metal exposure group exposed to soil containing low metal levels (Pb: 75 mg/kg; Cd: 0.4), and 3) high-metal exposure group exposed to soil (Pb: 3750; Cd: 6). After 1 year of exposure, the metal levels, Pb isotopic values, and molecular indicators were measured. Rats in the high-group showed significantly greater concentrations of Pb and Cd in tissues. Higher accumulation factors (tissue/soil) of Cd than Pb were observed in the liver, kidney, brain, and lung, while the factor of Pb was higher in the tibia. The obtained results of metal accumulation ratios (lung/liver) and stable Pb isotope ratios in the tissues indicated that the respiratory exposure would account for an important share of metal absorption into the body. Genome-wide methylation status and DNA methyltransferase (Dnmt 3a/3b) mRNA expressions in testis were higher in the high-group, suggesting that exposure to soil caused metal accumulation and epigenetic alterations in rats.

Adsorption and fractionation of Pt, Pd and Rh (defined here as platinum group elements, PGEs) onto the representative inorganic microparticles, including Fe2O3, MnO2, CaCO3, SiO2, Al2O3 and kaolinite in seawater were investigated. The effects of macromolecular organic compounds (MOCs) as the representatives of organic matter, including humic acids (HA), bovine serum albumin (BSA) and carrageenan, on the adsorption were also studied considering that organic matter is ubiquitous in seawater and indispensable to marine biogeochemical cycles. In the absence of MOCs, the representative mineral particles Fe2O3 and MnO2 had the strongest interaction with PGEs. The adsorption of PGEs onto the representative biogenic particles SiO2 and CaCO3 and lithogenic particles Al2O3 and kaolinite was similar or weaker than onto the mineral particles. MOCs inhibited the interaction between PGEs and the particles except for Pt and Pd onto the biogenic particles in artificial seawater. This impediment may be closely related to the interaction between particles, MOCs and elements. The partition coefficient (log Kd) of Pt was similar (∼4.0) in the presence of MOCs, indicating that the complexation between Pt and MOCs was less important than hydrolysis or adsorption onto the acid oxide particle surface. Rh tended to fractionate onto the mineral and lithogenic particles in the presence of HA and carrageenan, while Pd was more likely to fractionate onto the biogenic particles. However, BSA enhanced the fractionation tendency of Pd onto the mineral particles. The results indicate that the adsorption behavior of Pd onto inorganic particles was significantly affected by the composition or the type of MOCs. Hence, the interaction between PGEs and inorganic particles may be greatly affected by the macromolecular organic matter in the ocean.

Hematite nanoparticles (NPs) exist naturally and ubiquitously in soil, and they are always associated with soil organic matter by forming organic-inorganic complexes. In this work, hematite NPs coated with peat humic acid (HAₚₑₐₜ) and soil humic acid (HAₛₒᵢₗ) were chosen as sorbents for hydrophobic organic contaminants (HOCs) to simulate the sorption processes in soil. Ionizable pentachlorophenol (PCP) and non-ionizable phenanthrene (PHE) were selected as representative HOCs. Compared with sorption isotherms of uncoated hematite NPs, the coating of HA onto the surface of hematite NPs substantially increased its sorption affinity for PCP and PHE by about 1-2 orders of magnitude, and the increasing degree was positively correlated to the HA content. These phenomena emphasized the dominant role of HA in the sorption process. The reduced polarity and the introduction of functional groups contributed to the enhanced sorption of HOCs on HA-coated hematite NPs. Furthermore, HAₚₑₐₜ-hematite NPs showed higher sorption affinity for both PCP and PHE than HAₛₒᵢₗ-hematite NPs, which was mainly due to the lower polarity and higher hydrophobicity of HAₚₑₐₜ-hematite NPs. The sorption of PCP and PHE on HA-coated hematite NPs was inhibited obviously with increasing pH values and the pH effect on PCP sorption was more significant than that of PHE, due to the deprotonation of functional groups within adsorbed HA, the loose structure of adsorbed HA and the dissociation of PCP. Our findings elucidated the mechanisms involved in HOCs sorption processes by HA-hematite NPs and provided a theoretical basis for environmental remediation with natural NPs (e.g., hematite NPs).

Release of fluoride from Quaternary sediments produces F-contaminated groundwater which threatens the health of millions of people worldwide. Despite the mechanisms of fluoride release from sediments are documented by numerous studies, it remains poorly understood that whether indigenous microbes participate in or not for the formation of F-rich groundwater by releasing fluoride from aquifer sediments. A microcosm-based approach, geochemistry and techniques of microbiology and molecular ecology were conducted together to investigate these mechanisms. Results show that microbes are abundant in high [F] groundwater containing at least 1129 operational taxonomic units (OTUs), and indigenous microbes can have an essential role in the mobilization of fluoride in sediments collected from aquifers in a typical fluorosis area in China. It also shows that for the sediments in this study, fluoride release (ca. 2 mg/L) is coupled with elevated concentrations of Ca (△ = 75 mg/L), Mg (△ = 33 mg/L), Al (△ = 0.2 mg/L) and Mn (△ = 1.4 mg/L). This suggests that the fluoride may source from the dissolution of F-bearing carbonate minerals and/or Al-Mn hydroxides in a local acidic environment. The findings provide additional insights into the biogeochemical circulation of fluoride in natural environment, especially in groundwater system and the development of effective strategies for the management of F-contaminated groundwater worldwide.

Degrading aquatic organic pollutants efficiently is very important but strongly relied on the design of photocatalysts. Porous graphene could increase photocatalytic performance of ZnO nanoparticles by promoting the effective charge separation of electron-hole pairs if they can be composited. Herein, porous graphene, ZnO nanoparticles and porous graphene/ZnO nanocomposite were prepared by fine tuning of partial combustion, which graphene oxide imperfectly covered by the layered Zn salt was combusted under muffle furnace within few minutes. Resulting ZnO nanoparticles (32–72 nm) are dispersed uniformly on the surface of graphene sheets, the pore sizes of porous graphene are in the range from ∼3 to ∼52 nm. The synthesized porous graphene/ZnO nanocomposite was confirmed to show enhanced efficiency under natural sunlight irradiation compared with pure ZnO nanoparticles. Using porous graphene/ZnO nanocomposite, 100% degradation of methyl orange can be achieved within 150 min. The synergetic effect of photocatalysis and adsorption is main reason for excellent MO degradation of PG/ZnO nanocomposite. This work may offer a new route to accurately prepare porous graphene-based nanocomposite and open a door of their applications.

Graphene oxide (GO) has been demonstrated to be key component for diverse applications. However, their potential environmental reactivity, fate and risk have not been fully evaluated to date. In this study, we investigated the photochemical reactivity of four types of GO with different oxidation degrees in aqueous environment, and their related toxicity to two bacterial models Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was further compared. After UV-irradiation, a large amount of oxygen functional groups on GO were reduced and the electronic conjugations within GO were restored as indicated by UV–visible absorption spectra, X-ray photoelectron spectroscopy and Raman spectroscopy analysis. Moreover, the higher the oxidation degree of the pristine GO was, the more obvious of the photo-transformation changes were. In order to further reveal the photochemical reactivity mechanisms, the reactive oxygen species (ROS) generation of GO was monitored. The quantity of ROS including singlet oxygen (1O2), superoxide anions (O2·-), and hydroxyl radicals (·OH) increased with increasing oxidation degree of GO, which was in accordance with the previous characterization results. Scanning electron microscopy and cell growth analyses of E. coli and S. aureus showed that the photochemical transformation enhanced the toxicity of GO, which might be due to an increase in functional group density. The higher conductivity of the reduced graphene oxide (RGO) was responsible for its stronger toxicity than GO through membrane damage and oxidative stress to bacteria. This study revealed that the oxidation degrees play important roles in photochemical transformation and the resulting toxicity of GO, which is helpful for understanding the environmental behaviors and risks of GO in aquatic environments.

Iron fertilizers are worthy to be studied due to alleviate the Fe deficiency. Different forms of iron oxide nanoparticles are selected to better understand possible particle applications as an Fe source for crop plants. In this study, we assessed the different effects of γ-Fe2O3 and Fe3O4 NPs on the physiology and fruit quality of muskmelon plants in a pot experiment for five weeks. Results showed that no increased iron content was found under NPs treatment in root, stem, leaf and fruit, except 400 mg/L Fe3O4 NPs had a higher iron content in muskmelon root. With the extension of NPs exposure, both γ-Fe2O3 and Fe3O4 NPs began to promote plant growth. In addition, γ-Fe2O3 and Fe3O4 NPs could increase chlorophyll content at a certain stage of exposure. Happily, 200 mg/L γ-Fe2O3 NPs and 100, 200 mg/L Fe3O4 NPs significantly increased fruit weight of muskmelon by 9.1%, 9.4% and 11.5%. It is noteworthy that both γ-Fe2O3 and Fe3O4 NPs caused positive effects on VC content, particularly 100 mg/L Fe3O4 NPs increased the VC content by 46.95%. To the best of our knowledge, little research has been done on the effect of nanoparticles on the whole physiological cycle and fruit quality of melon. The assessment of physiology and fruit quality of muskmelon plants in vitro upon γ-Fe2O3 and Fe3O4 NPs exposure could lay a foundation for NPs potential impact at every growth period of muskmelon plants.