Surface characteristics and adsorption properties of polypropylene microplastics by ultraviolet irradiation and natural aging.

The vast application and deep integration of plastic commodity with our human lives raise a great concern about the ubiquitous microplastics (MPs) in nature, yet the environmental behavior of MPs remain unclear. As a main type and candidate of MPs, pristine polypropylene MPs (PP-MP-Pris), as well as the influence of ultraviolet (UV) irradiation on the degree of aging and surface characteristics, were characterized quantitatively by Fourier infrared spectroscopy, scanning electron microscopy, contact angle meter, automatic specific surface area and pore analyzer and laser particle analyzer, with natural aged PP-MPs (PP-MP-Age) as comparison. The carbonyl index (CI) of UV aged PP-MPs (PP-MP-U) was increased with extension of exposure time, while biofilm with abundant functional groups and the maximum CI value were the characteristics of PP-MP-Age. Moreover, the adsorption capacity of PP-MP-U for crystal violet (CV) was increased and reached the maximum after 30 days, while that of PP-MP-Age was weakened, probably due to the enhanced hydrophilicity and the shedding of calcium carbonate (CaCO3) during the natural aging process, which was demonstrated by hydrochloric acid treatment, indicating the vital involvement of CaCO3. Moreover, the better fitting to PSO kinetics and Freundlich isotherm models indicated that the multilayered and non-homogeneous surface adsorption was acted as the rate-controlling step. Furthermore, the positive values of ΔGθ, ΔHθ and ΔSθ indicated that the adsorption was a non-spontaneous, endothermic process with increased degree of the freedom on the interface of PP-MPs and CV solution. The presence of divalent salts inhibited CV adsorption, demonstrating that electrostatic attraction played a major role in CV capture. The hydrophobic interaction, micropore filling, hydrogen bonding, and π - π conjugation were possible involved. This study is of great significance for better understanding the complex pollution of MPs and its potential environmental risks in the future.

Aging and adsorption behavior of PP-MPs for methylene blue and tetracycline in unitary and binary systems.

The omnipresence of microplastics (MPs) around the world has attracted extensive attention in the past decade with more focuses on the interactions of standard MPs without additives in regular shapes and individual pollutant, whereas the actual MPs containing various additives in irregular shapes and complex pollutants are often co-occurrence in the environments. In this paper, the adsorption performance of disposable polypropylene (PP) cups-based MPs subjected to ultraviolet irradiation was investigated in unitary and binary water matrices. The surface characteristics were analyzed and the experimental data of adsorption were fitted by various kinetic and isotherm models, and the results indicated that more cracks and oxygen-containing functional groups with decreased hydrophobicity were produced with aging, and electrostatic attraction and hydrogen bonding dominated methylene blue (MB) and tetracycline (TC) capture in the individual system. Moreover, pseudo-second order kinetic model better described the adsorption processes. In the binary system, the co-existence of TC promoted MB uptake, while the presence of MB inhibited TC capture. In addition, TC adsorption was enhanced by Ca2+, maybe due to its complexation effect, while the presence of mono- and divalent inorganic salts inhibited MB capture. This research provides useful insights for the fate of PP-MPs and organic pollutants in the complex environments.

Aging and characterization of disposable polypropylene plastic cups based microplastics and its adsorption for methylene blue.

Microplastics (MPs) as emerging pollutants are of increasing concern, due to their ubiquitous, uncertain, and complex environmental impacts. Different from the standard spherical MPs without additives, here polypropylene microplastics (PP-MPs) in flake derived from the disposable plastic cup in food-grade in daily life were studied. The characterization of PP-MPs demonstrated that the carbonyl index represented the aging degree was enhanced from 0.26 significantly to 0.82 after 10 days, and the aging process fitted well with pseudo-first-order kinetic. Moreover, the crystallinity degree, polarity and surface negative charges were enhanced, while the hydrophobicity was decreased. The adsorption behavior of PP-MPs toward methylene blue (MB), and the impacts of various pHs, salinities, and humic acid in aquatic environments were also explored. The pseudo-second-order kinetic, Henry and Sips isotherm models provided a good correlation with the experimental data, indicating that the rate-limiting step was closely related with the complex surface adsorption, and the hydrophobic partitioning, polar interaction, electrostatic attraction, and hydrogen bonding were possibly involved in the adsorption. These exhaustive experiments aim to provide a theoretical basis for assessing and better understanding the environmental behavior of disposable PP plastic cups in nature.

Identification of naturally weathering microplastics and their interactions with ion dyes in aquatic environments.

Here, naturally weathering plastics were collected and identified to understand the effect of the weathering conditions on their properties. The adsorption and desorption of crystal Violet (CV), a candidate of cationic organic pollutant, on microplastics (MPs) under various environmental conditions were simultaneously explored. The first type was the aged polyethylene (PE-MPs), which exhibited a fibrous structure with a smoother and uniform surface attached some flaps, while the second type was recognized as the aged polypropylene (PP-MPs), which showed a lamellar structure with less smooth and distorted texture surface attached with fragments and small grains. The experiment data fitted well with the pseudo-second-order kinetic and Freundlich isotherm models. The possible interactions between CV and MPs included electrostatic attraction, hydrogen bonding and hydrophobic interactions. This study demonstrates that the high possibility of transport ionic pollutants from fresh water to ocean by the naturally weathering microplastics, highlighting their potential risk in various environments.

Occurrence, seasonal variation and inhalation exposure of atmospheric organophosphate and pyrethroid pesticides in an urban community in South China.

The shift in pesticide usage patterns demands a better understanding of the occurrence, fate and exposure risk of atmospheric current-use pesticides (CUPs). Air samples collected in different seasons from an urban community in Guangzhou, China were analyzed to investigate seasonal variation, gas-particle partitioning and inhalation exposure of atmospheric organophosphate and pyrethroid pesticides. Chlorpyrifos and eight pyrethroids were detected in the air samples and the total concentrations of the nine CUPs ranged from 150 to 3816 pg m(-3). Chlorpyrifos and cypermethrin were the most dominant CUPs detected in the atmosphere, accounting for 68% and 15% of the total CUPs, respectively. Seasonal variation in concentration was observed for most CUPs, with peak concentrations occurring in summer and fall, which was consistent with their application patterns. Partitioning of chlorpyrifos between gas and particle phases was also seasonally-dependent, with more chlorpyrifos found in the gas phase in summer and fall. Additionally, gas-particle partitioning analysis suggested that chlorpyrifos might experience long-range transport. Evaluation of potential exposure from inhalation of atmospheric CUPs suggested that children, toddlers and infants had the highest exposure, but the risk quotients were low for all age groups when annual average concentrations were used as exposure metrics. Exposure risk was higher in summer and fall than the annual average level due to higher atmospheric pesticide concentrations, longer exposure times and more pesticides being in the gaseous form.

Novel synthesis of methoxymethyl benzene by electrochemical coupling reaction of toluene with methanol in ionic liquid media.

An ionic liquid (1-butyl-3-methylimidazolium dibutyl phosphate) was prepared and characterized by cyclic voltammogram (CV) and Fourier transform infrared spectrometer (FT-IR). The ionic liquid exhibited good catalytic activity for the electrochemical reaction of toluene with methanol assisted with a pair of porous graphite plane electrodes and product yield higher than 56% was observed. In addition, the electrochemical process was detected by UV-vis spectrum and the products were analyzed by gas chromatography/mass spectrometry (GC/MS). According to the experimental results, a possible free radical reaction mechanism was proposed. It may be concluded that a simply and feasible electrochemical coupling reaction at room temperature and atmospheric pressure may be possible. Compared with methyl tert-butyl ether (MTBE), the main product (methoxymethyl benzene) used as booster to improve fuel combustion was also studied.

Electrochemical pilot-scale plant for oil field produced wastewater by M/C/Fe electrodes for injection.

Oil field produced water by separated with crude oil were treated by an electrochemical process in laboratory pilot-scale plant, using double anodes with active metal (M) and graphite (C) and iron as cathode and a noble metal content catalyst with big surface. Due to the strong oxidizing potential of the chemicals produced (Cl(2), O(2), OCl(-), HO and so on), when the wastewater pass through the laboratory pilot-scale plant the organic pollutants including bacteria were oxidized and coagulated by produced M(n+) ion. It can be concluded that the catalytic electrochemical treatment of oil field produced wastewater is effective. Both chemical oxygen demand (COD) and biochemical oxygen demand (BOD) were reduced by over 90% in 6 min, suspense solids (SS) by 99%, Ca(2+) content by 22%, corrosion rate by 98% and bacteria (sulphate reducing bacteria (SRB), saprophytic bacteria (TGB) and iron bacteria) by 99% in 3 min under 15V/120A. These results indicate that this catalytic electrochemical method could be used for effective oil field wastewater treatment for injection purpose.