No abstract

No abstract

Plastic debris, in particular, microplastics and nanoplastics, is becoming an emerging class of pollutants of global concern. Aging can significantly affect the physicochemical properties of plastics, and therefore, may influence the fate, transport, and effects of these materials. Here, we show that aging by UV or O3 exposure drastically enhanced the mobility and contaminant-mobilizing ability of spherical polystyrene nanoplastics (PSNPs, 487.3 ± 18.3 nm in diameter) in saturated loamy sand. Extended Derjaguin–Landau–Verwey–Overbeek calculations and pH-dependent transport experiments demonstrated that the greater mobility of the aged PSNPs was mainly the result of surface oxidation of the nanoplastics, which increased not only the surface charge negativity, but more importantly, hydrophilicity of the materials. The increased mobility of the aged PSNPs significantly contributed to their elevated contaminant-mobilizing abilities. Moreover, aging of PSNPs enhanced the binding of both nonpolar and polar contaminants, further increasing the contaminant-mobilizing ability of PSNPs. Interestingly, aging enhanced binding of nonpolar versus polar compounds via distinctly different mechanisms: increased binding of nonpolar contaminants (tested using pyrene) was mainly the result of the modification of the polymeric structure of PSNPs that exacerbated slow desorption kinetics; for polar compounds (4-nonylphenol), aging induced changes in surface properties also resulted in irreversible adsorption of contaminants through polar interactions, such as hydrogen bonding. The findings further underline the significant effects of aging on environmental fate and implications of nanoplastics.

Translating the unique characteristics of individual nanoscale components into macroscopic materials such as membranes or sheets still remains a challenge, as the engineering of these structures often compromises their intrinsic properties. Here, we demonstrate that the highly active carbonaceous nanofibers (CNFs), which are prepared through a template-directed hydrothermal carbonization process, can be used as a versatile nanoscale scaffold for constructing macroscopic multifunctional membranes. In order to demonstrate the broad applicability of the CNF scaffold, we fabricate a variety of CNF-based composite nanofibers, including CNFs-Fe(3)O(4), CNFs-TiO(2), CNFs-Ag, and CNFs-Au through various chemical routes. Importantly, all of them inherit unique dimensionality (high aspect ratio) and mechanical properties (flexibility) of the original CNF scaffolds and thus can be assembled into macroscopic free-standing membranes through a simple casting process. We also demonstrate the wide application potentials of these multifunctional composite membranes in magnetic actuation, antibiofouling filtration, and continuous-flow catalysis.

Abstract. Soil carbon (C) is the largest C pool in the terrestrial biosphere and includes both inorganic and organic components. Studying patterns and controls of soil C help us to understand and estimate potential responses of soil C to global change in the future. Here we analyzed topsoil data of 81 sites obtained from a regional survey across grasslands in the Inner Mongolia and on the Tibetan Plateau during 2006-2007, attempting to find the patterns and controls of soil inorganic carbon (SIC) and soil organic carbon (SOC). The averages of inorganic and organic carbon in the topsoil (0-20 cm) across the study region were 0.38 % and 3.63 %, ranging between 0.00-2.92 % and 0.32-26.17 % respectively. Both SIC and SOC in the Tibetan grasslands (0.51 % and 5.24 % respectively) were higher than those in the Inner Mongolian grasslands (0.21 % and 1.61 %). Regression tree analyses showed that the spatial pattern of SIC and SOC were controlled by different factors. Chemical and physical processes of soil formation drive the spatial pattern of SIC, while biotic processes drive the spatial pattern of SOC. SIC was controlled by soil acidification and other processes depending on soil pH. Vegetation type is the most important variable driving the spatial pattern of SOC. According to our models, given the acidification rate in Chinese grassland soils in the future is the same as that in Chinese cropland soils during the past two decades: 0.27 and 0.48 units per 20 yr in the Inner Mongolian grasslands and the Tibetan grasslands respectively, it will lead to a 30 % and 53 % decrease in SIC in the Inner Mongolian grasslands and the Tibetan grasslands respectively. However, negative relationship between soil pH and SOC suggests that acidification will inhibit decomposition of SOC, thus will not lead to a significant general loss of carbon from soils in these regions.

Bound-residue formation is a major dissipation process of most organic xenobiotics in soil. However, both the formation and nature of bound residues of tetrabromobisphenol A (TBBPA) in soil are unclear. Using a 14C-tracer, we studied the fate of TBBPA in an oxic soil during 143 days of incubation. TBBPA dissipated with a half-life of 14.7 days; at the end of incubation, 19.6% mineralized and 66.5% formed bound residues. Eight extractable metabolites were detected, including TBBPA methyl ethers, single-ring bromophenols, and their methyl ethers. Bound residues (mostly bound to humin) rapidly formed during the first 35 days. The amount of those humin-bound residues then quickly decreased, whereas total bound residues decreased slowly. By contrast, residues bound to humic acids and fulvic acids increased continuously until a plateau was reached. Ester- and ether-linked residues accounted for 9.6-27.0% of total bound residues during the incubation, with ester linkages being predominant. Residues bound via ester linkages consisted of TBBPA, TBBPA monomethyl ether, and an unknown polar compound. Our results indicated that bound-residue formation is the major pathway of TBBPA dissipation in oxic soil and provide first insights into the chemical structure of the reversibly ester-linked bound residues of TBBPA and its metabolites.

Nanoplastics (NPs) are becoming an emerging pollutant of global concern. A potential risk is that NPs may serve as carriers to increase the spreading of coexisting contaminants. In this study, we examined the effects of polystyrene nanoplastics (PSNPs, 100 nm), used as a model NP, on the transport of five organic contaminants of different polarity in saturated soil. The presence of low concentrations of PSNPs significantly enhanced the transport of nonpolar (pyrene) and weakly polar (2,2',4,4'-tetrabromodiphenyl ether) compounds, but had essentially no effects on the transport of three polar compounds (bisphenol A, bisphenol F, and 4-nonylphenol). The strikingly different effects of NPs on the transport of nonpolar/weakly polar versus polar contaminants could not be explained with different adsorption affinities, but was consistent with the polarity-dependent extents of desorption hysteresis. Notably, desorption hysteresis was only observed for nonpolar/weakly polar contaminants, likely because nonpolar compounds tended to adsorb in the inner matrices of glassy polymeric structure of polystyrene (resulting in physical entrapment of adsorbates), whereas polar compounds favored surface adsorption. This hypothesis was verified with supplemental adsorption and desorption experiments of pyrene and 4-nonylphenol using a dense, glassy polystyrene polymer and a flexible, rubbery polyethylene polymer. Overall, the findings of this study underscore the potentially significant environmental implication of NPs as contaminant carriers.

A carbon-14 radiotracer-based study revealed that water promoted mineralization and photo-oxidation of polystyrene nanoplastics with significant amounts of carbon leached out.