Multipath diffusion process and spatial accumulation simulation of Cd in lead-zinc mining areas.

This study combined process simulation and actual measurement to construct a multipath diffusion and spatial accumulation model of Cd in a typical lead-zinc mining area through accuracy and root mean square error(RMSE) analysis. The results indicated that (1) the diffusion of Cd was in a quadratic inverse proportional relationship with the distance from the pollution source within watershed. The average annual atmospheric Cd sedimentation in study area was 0.71 * 10-6 g and the contribution of runoff diffusion to Cd exceeded 80%. (2) With the increase in the concentration range of Cd content (k) carried by unit runoff sediment, the model accuracy and RMSE showed decreasing trends. However, when the lower and upper limits of k were 10% and 90%, the model accuracy reached 75%. (3) Two sub-watersheds with same dominant wind direction but different runoff directions were selected to verify the model accuracy, indicating that the model construction method can precisely simulate the spatial accumulation of Cd in similar mining areas. The results provide a scientific basis for the prevention of heavy metal diffusion in lead-zinc mines. Future research should focus on the migration pathways of heavy metals through vertical infiltration caused by rainfall to further optimise the model structure and accuracy.

Capillary rise behavior of lubricant in micropores with spiral bulge structures.

The highly efficient exudation of lubricant in porous self-lubricating materials significantly influences the formation of self-lubricating films. In this paper, micropores with inner spiral bulge structures are considered, and their influence on the capillary behaviors of the lubricant is discussed to reveal the capillary rising mechanism. The results show that the Taylor capillary lift phenomenon is produced in the spiral bulge structure of the micropore, and the capillary lift force is enhanced. The spiral structure decreases the effective diameter of micropores. The magnitudes of the pressure and velocity in the spiral structure pores are larger than those in smooth pores. The liquid in the upper part of the micropores forms a velocity vortex during its upward rotation along the spiral channel, which promotes the capillary rising behavior. For smaller pitches, the velocity vortex increases, and the rising speed of the lubricant grows. The inner spiral bulge structure gives the micropores an excellent capillary rising ability. The quantitative characterization and mechanism reveal that the capillary rising behavior can be used to guide the bionic designs of pores in self-lubricating materials.

Characterization and Tribological Performances of Graphene and Fluorinated Graphene Particles in PAO.

Graphene has been widely used as a lubricating additive to reduce the energy consumption of engines and improve fuel economy because of its unique crystal structure. Herein, graphene (GR) and fluorinated graphene (F-GR) nanoparticles were prepared by ball milling and liquid-phase exfoliation. The SEM/EDS, HRTEM, XPS, Raman spectrometer, X-ray spectrometer, FTIR were used to investigate the morphologies, surface groups, and crystal structure of two kinds of graphene materials. The influence of loads on the tribological properties of two kinds of particles was investigated in Poly Alpha Olefin (PAO6) using a UMT-2 reciprocating tribometer. Results showed that the crystal structure of GR is better than F-GR. F-GR can improve the lubrication performance of PAO6. For PAO6 containing 1 wt% F-GR at 10 N, the average friction coefficient and average wear rate decreased by 12.3% and 87% relative to pure PAO6, respectively. However, the high load resulted in an inconspicuous anti-wear and anti-friction effect. The influence of F-GR on the tribological behavior of PAO6 was more substantial than that of GR. The friction and wear mechanisms attributed to F-GR quickly entered the interface between the friction pairs. Friction-induced F-GR nanosheets mainly took the tribo-chemical reactions to participate in the lubrication film formation and helped achieve a low friction coefficient and wear rate.

LDPE and HDPE Microplastics Differently Affect the Transport of Tetracycline in Saturated Porous Media.

The accumulation of microplastics (MPs) in soil and sediments may influence the penetration of contaminants into subsurface environments. However, little attention has been paid to comparing the different roles of two common polyethylene (PE) types-low-density polyethylene (LDPE) and high-density polyethylene (HDPE). In this study, the transport behaviors of tetracycline in saturated quartz sand columns in the presence and absence of these two MPs were investigated, respectively. The results showed that both types of PE MPs restrained the mobility of tetracycline at neutral conditions, while such detrimental effects were weak at acid and alkaline conditions. The degree of nonequilibrium adsorption was higher, and tetracycline transferred easier to the kinetic site for the existence of LDPE than of HDPE. The increased roughness and Brunauer-Emmett-Teller (BET) surface areas, more negative zeta potentials and the formation of oxygen function groups on the surface of MPs after UV-weathering intensified the retardation of tetracycline transport. This study revealed that the PE type and weathering should be taken into account in risk assessment, along with the solution chemistry.

Cotransport of naphthalene with polystyrene nanoplastics (PSNP) in saturated porous media: Effects of PSNP/naphthalene ratio and ionic strength.

As emerging contaminants of global concern, nanoplastics are significantly potential carriers of hydrophobic organic compounds in aquatic and soil environment. However, little is known about the interactions between the transports of nanoplastics and organic contaminants in porous media. In this study, the cotransport of naphthalene with polystyrene nanoplastics (PSNP) in saturated sand columns as influenced by the PSNP/naphthalene ratio and ionic strength (IS) was investigated. The presence of PSNP dramatically enhanced the mobility of naphthalene at low IS (0.5 mM), but such effect was prohibited at high IS (5 mM and 50 mM). The mobility of PSNP in the sand column was higher when it was solely exist in the pore-water than that when in the presence of naphthalene, because of the charge-shielding effect. This work showed that the coexistence of PSNP and naphthalene would influence the mobility of each other in the saturated porous media, which highly related to their concentration ratio and IS levels.

Novel Synthesis of Cu-Schiff Base Complex@Metal-Organic Framework MIL-101 via a Mild Method: A Comparative Study for Rapid Catalytic Effects.

The use of metal complex immobilized/decorated porous materials as catalysts has found various applications. As such, finding a new and mild method for synthesis of metal complex immobilized over porous material is of great interest. Immobilized porous materials for styrene oxidation were reported in this work. Immobilized porous material of Cu-Schiff base complex @MIL-101 were described, in which immobilized Cu-Schiff base complex within super cage of a metal-organic framework (MOF)-based porous material, chromium (III) terephthalate MIL-101. They were systematically characterized by using elemental analysis, powder X-ray diffraction, fourier transform infrared spectroscopy, N2 absorption-desorption, and so on, also used as catalyst for the selective oxidation of styrene to benzaldehyde. Comparatively, the immobilized heterogeneous catalyst of Cu-Schiff base complex@MIL-101 acted as an efficient heterostructure catalyst in the oxidation of styrene to benzaldehyde up to six cycles, and showed superior activity for styrene oxidation over MIL-101.

Interface decoration of exfoliated MXene ultra-thin nanosheets for fire and smoke suppressions of thermoplastic polyurethane elastomer.

Thermoplastic polyurethane (TPU) has broad applications as lightweight materials due to its multiple advantages and unique properties. Nevertheless, toxicity emission under fire conditions remains a major concern, particularly in building fire scenarios. To circumvent the problem, it is imperative that an effective flame retardant is sought to suppress the flame and release of combustion/smoke products whilst maintaining the favorable material properties of TPU. In the current work, a simple method is proposed for the preparation and utilization of cetyltrimethyl ammonium bromide (CTAB) and tetrabutyl phosphine chloride (TBPC) modified Ti3C2 (MXene) ultra-thin nanosheets. During the cone calorimeter tests, significant reduction in peak heat release rate (51.2% and 52.2%), peak smoke production rate (57.1% and 57.4%), peak CO production (39.4% and 41.6%) and peak CO2 production (49.7% and 51.7%) were recorded by the mere introduction of 2 wt.% CTAB-Ti3C2 and TBPC-Ti3C2 to TPU. These superior fire safety properties resulting from the significant reduction of the fire, smoke and toxicity hazards are attributed to the excellent dispersion, catalytic and barrier effect of Ti3C2 ultra-thin nanosheets in TPU. Future applications of exfoliated MXene nanosheets as flame retardant appear to be very promising.

Removal of phenanthrene and pyrene from contaminated sandy soil using hydrogen peroxide oxidation catalyzed by basic oxygen furnace slag.

Soil contamination with polycyclic aromatic hydrocarbons (PAHs) is a serious problem in Northeast China, especially in the steel industrial area. The objective of this study was to evaluate the feasibility of using basic oxygen furnace (BOF) slag to activate the Fenton-like remediation of PAH-contaminated soil to achieve the objectives of "waste control by waste" and "resource recycling" in Chinese steel industry. The effects of BOF slag dosages, H2O2 concentrations, and exothermicity-driven evaporation were evaluated with respect to the removal efficiencies of phenanthrene (Phe) and pyrene (Pyr). Results indicated that PAH oxidation was proportional to the BOF slag dosages and was increased exponentially with H2O2 concentrations. Evaporation due to increasing temperature caused by exothermic reaction played an important role in total soil PAH losses. The sequential Fenton-like oxidation with a 3-times application of 15% H2O2 and the same BOF slag repeatedly used were able to remove 65.87% of Phe and 58.33% of Pyr, respectively. Soluble iron oxides containing in BOF slag were reduced, while amorphous iron oxide concentration remained stable during the repeated Fenton-like process. Column study mimics real field applications showing high removal efficiencies of Phe (36.05-83.20%) and Pyr (21.79-68.06%) in 30-cm depth of soil profile. The tests on soluble heavy metal concentrations after the reactions with high slag dosage or high H2O2 concentration confirmed that BOF slag would not cause heavy metal contamination. Consequently, BOF slag may provide an efficient way for enhancing the Fenton-like based remediation of heavily PAH-polluted soil with little risk on collateral heavy metal contamination. However, an external gas collection and purification equipment would be essential to eliminate the evaporated PAHs.

Comparative Studies on Thermal, Mechanical, and Flame Retardant Properties of PBT Nanocomposites via Different Oxidation State Phosphorus-Containing Agents Modified Amino-CNTs.

High-performance poly(1,4-butylene terephthalate) (PBT) nanocomposites have been developed via the consideration of phosphorus-containing agents and amino-carbon nanotube (A-CNT). One-pot functionalization method has been adopted to prepare functionalized CNTs via the reaction between A-CNT and different oxidation state phosphorus-containing agents, including chlorodiphenylphosphine (DPP-Cl), diphenylphosphinic chloride (DPP(O)-Cl), and diphenyl phosphoryl chloride (DPP(O3)-Cl). These functionalized CNTs, DPP(Ox)-A-CNTs (x = 0, 1, 3), were, respectively, mixed with PBT to obtain the CNT-based polymer nanocomposites through a melt blending method. Scanning electron microscope observations demonstrated that DPP(Ox)-A-CNT nanoadditives were homogeneously distributed within PBT matrix compared to A-CNT. The incorporation of DPP(Ox)-A-CNT improved the thermal stability of PBT. Moreover, PBT/DPP(O3)-A-CNT showed the highest crystallization temperature and tensile strength, due to the superior dispersion and interfacial interactions between DPP(O3)-A-CNT and PBT. PBT/DPP(O)-A-CNT exhibited the best flame retardancy resulting from the excellent carbonization effect. The radicals generated from decomposed polymer were effectively trapped by DPP(O)-A-CNT, leading to the reduction of heat release rate, smoke production rate, carbon dioxide and carbon monoxide release during cone calorimeter tests.

Quantification of ozone exposure- and stomatal uptake-yield response relationships for soybean in Northeast China.

High ground-level O3 is a new threat to agricultural production in Northeast China with the increasing ambient O3 concentration. Little is known about its impacts on soybean production in this key agricultural region. Accumulated O3 exposure-response and stomatal O3 flux-response relationships were developed during two continuous growing seasons to evaluate O3-induced yield reduction of four typical soybean cultivars in Northeast China. Results showed that critical levels of AOT40 (accumulated hourly O3 concentrations over a threshold of 40nmol·mol-1), SUM06 (sum of all hourly average O3 concentrations over 0.06µmol·mol-1) and W126 (sum of O3 concentrations weighted by a sigmoidal function) in relation to 5% reduction in relative seed yield were 4.2, 7.6 and 6.8µmol·mol-1·h, respectively. The effect of O3 on plants was influenced by leaf position in canopy. An improved Jarvis stomatal conductance model including leaf (node) position fitted well with field measurements. The best linear relationship between stomatal O3 flux and relative soybean yield was obtained when phytotoxic ozone dose was integrated over a threshold of 9.6nmol·m-2·s-1 (POD9.6) to represent the detoxification capacity of soybean. POD9.6 and the commonly used POD6 in relation to 5% reduction in relative seed yield of soybean were 0.9mmol·m-2 and 1.8mmol·m-2, respectively. O3 concentrations above ~38nmol·mol-1 contributed to POD9.6 and caused seed yield loss in soybean. Current annual yield loss of soybean at ambient O3 was estimated to range between 23.4% and 30.2%. The O3 dose-response relationships and corresponding thresholds obtained here will benefit regional O3 risk assessment on soybean production in Northeast China.

Concentration- and flux-based ozone dose-response relationships for five poplar clones grown in North China.

Concentration- and flux-based O3 dose-response relationships were developed for poplars in China. Stomatal conductance (gs) of five poplar clones was measured to parameterize a Jarvis-type multiplicative gs model. The maximum gs and other model parameters varied between clones. The strongest relationship between stomatal O3 flux and total biomass was obtained when phytotoxic ozone dose (POD) was integrated using an uptake rate threshold of 7 nmol m(-2) s(-1). The R(2) value was similar between flux-based and concentration-based dose-response relationships. Ozone concentrations above 28-36 nmol mol(-1) contributed to reducing the biomass production of poplar. Critical levels of AOT40 (accumulated O3 exposure over 40 nmol mol(-1)) and POD7 in relation to 5% reduction in total biomass for poplar were 12 µmol mol(-1) h and 3.8 mmol m(-2), respectively.

Ground-level O3 pollution and its impacts on food crops in China: a review.

Ground-level ozone (O3) pollution has become one of the top environmental issues in China, especially in those economically vibrant and densely populated regions. In this paper, we reviewed studies on the O3 concentration observation and O3 effects on food crops throughout China. Data from 118 O3 monitoring sites reported in the literature show that the variability of O3 concentration is a function of geographic location. The impacts of O3 on food crops (wheat and rice) were studied at five sites, equipped with Open Top Chamber or O3-FACE (free-air O3 concentration enrichment) system. Based on exposure concentration and stomatal O3 flux-response relationships obtained from the O3-FACE experimental results in China, we found that throughout China current and future O3 levels induce wheat yield loss by 6.4-14.9% and 14.8-23.0% respectively. Some policies to reduce ozone pollution and impacts are suggested.

Methods and techniques for measuring gas emissions from agricultural and animal feeding operations.

Emissions of gases from agricultural and animal feeding operations contribute to climate change, produce odors, degrade sensitive ecosystems, and pose a threat to public health. The complexity of processes and environmental variables affecting these emissions complicate accurate and reliable quantification of gas fluxes and production rates. Although a plethora of measurement technologies exist, each method has its limitations that exacerbate accurate quantification of gas fluxes. Despite a growing interest in gas emission measurements, only a few available technologies include real-time, continuous monitoring capabilities. Commonly applied state-of-the-art measurement frameworks and technologies were critically examined and discussed, and recommendations for future research to address real-time monitoring requirements for forthcoming regulation and management needs are provided.

[Influence of ozone on snap bean under ambient air in two sites of northern China].

Tropospheric ozone (O3) has been assumed the most phytotoxic air pollutant and the snap bean (Phaseolus vulgaris L.) is known to be an ozone-sensitive species. Two genotypes (R123, ozone-tolerance, S156, ozone-sensitivity) of snap bean were explored in three places. The objective of this study was to evaluate whether the snap bean was influenced under the current ambient ozone concentration. The findings indicated that the leaves of bean grown at Research Center for Eco-Environmental Sciences (RCEES), Chinese Academy of Sciences and ChangPing showed visible ozone symptoms under the ambient ozone concentration, and the averaged ozone injury proportion in S156 was 23.5% higher than R123 during the entire growth season. The ozone damage to the snap bean depends on the plant growing stages. The injury symptoms appeared just after flowering, increased from the stages of flowering to pod formation, and reached the maximum at the stages of pod maturation. The ratio of S156/R123 in pod yield was 0.48, and 0.24 and 0.73 in the RCEES, ChangPing and Harbin, respectively. The ratio close to 1 was assumed that the plant growth is not affected by ozone, and the lower ratio is, the more damage caused by ozone. Obviously, the current ambient ozone concentration of Beijing area has significantly caused the yield loss of snap bean.

Evidence of widespread ozone-induced visible injury on plants in Beijing, China.

Despite the high ozone levels measured in China, and in Beijing in particular, reports of ozone-induced visible injury in vegetation are very scarce. Visible injury was investigated on July and August 2013 in the main parks, forest and agricultural areas of Beijing. Ozone injury was widespread in the area, being observed in 28 different species. Symptoms were more frequent in rural areas and mountains from northern Beijing, downwind from the city, and less frequent in city gardens. Among crops, injury to different types of beans (genera Phaseolus, Canavalia and Vigna) was common, and it was also observed in watermelon, grape vine, and in gourds. Native species such as ailanthus, several pines and ash species were also symptomatic. The black locust, the rose of Sharon and the Japanese morning glory were among the injured ornamental plants. Target species for broader bio-monitoring surveys in temperate China have been identified.

Physical and thermal characteristics of dairy cattle manure.

Greenhouse and regulated gas emissions from animal waste are naturally mediated by moisture content and temperature. As with soils, emissions from manure could be readily estimated given the physical, hydraulic, and thermal properties are described by models and microbes and nutrients are not limiting factors. The objectives of this study were to measure and model physical, hydraulic, and thermal properties of dairy manure to support advanced modeling of gas and water fluxes in addition to solute, colloid, and heat transport. A series of soil science measurement techniques were applied to determine a set of fundamental properties of as-excreted dairy cattle manure. Relationships between manure dielectric permittivity and volumetric water content (θ) were obtained using time-domain reflectometry and capacitance-based dielectric measurements. The measured water retention characteristic for cattle manure was similar to organic peat soil. The unsaturated hydraulic conductivity function of dairy manure was inferred from inverse numerical fitting of laboratory manure evaporation results. The thermal properties of dairy manure, including thermal conductivity, thermal diffusivity, and bulk volumetric heat capacity, were also determined using three penta-needle heat pulse probes. The accuracy of the heat capacity measurements was determined from a comparison of theoretical θ, estimated from the measured thermal properties with that determined by the capacitance-based dielectric measurement. These data represent a novel and unique contribution for advancing prediction and modeling capabilities of gas emissions from cattle manure, although the uncertainties associated with the complexities of shrinkage, surface crust formation, and cracking must also be considered.

[Effects of elevated O3 concentration on nitrogen in greening tree species in southern China].

Numerous studies have indicated that rising ozone (O3) in the troposphere significantly decreased the photosynthesis and the activity of Rubisco enzyme. So it can be inferred that the N uptake and distribution within the plants could be affected by elevated O3. In this study, ten greening woody species, widely distributed in subtropical China, were exposed to charcoal-filtered air (CF, less than 20 nL · L(-1)) and elevated O3 (E-O3, mean concentration of 150 nL · L(-1)) in open top chambers. The results showed that E-O3 significantly reduced the leaves biomass in Liquidamba formosana by 20.9%, the stem biomass in Liriodendron chinense by 21.4%, the root biomass in L. formosana and L. chinense by 24.2% and 32.5%, respectively. E-O3 significantly affected the N concentration in the stem but not those in leaves and root. The N uptakes in the whole tree (Nlu), the leaves and the root were significantly affected by E-O3. Compared to CF, E-O3 significantly reduced the Nlu in L. chinense by 28.4% and Schima superba by 22.7% but significantly increased the Nlu in Neolitsea sericea by 15.5%. Elevated O3 concentration had no significant influence on N distribution within the plants across the selected 10 tree species.

Qualitative analysis of the stability of a continuous vermicomposting system.

A mathematical model was established to describe ecological relationships in a continuous vermicomposting system. The distributions of organic matter, microbes and earthworms on non-dimensional specific growth rates were simulated. The range of specific growth rates were visualized utilizing three-dimensional reconstruction technology. The stability of a vermicomposting system was not influenced by the initial concentrations of microbes and earthworms, only their species. The coordinates of the stable point depended on the dilution rate and initial amount of organic matter. The method described could be help for establishing a stable continuous vermicomposting system.