Secondary Oxidation Processes Research Articles

CHARACTERIZATION OF FINE CARBONACEOUS AEROSOLS FROM THE EASTERN MEDITERRANEAN: CONTRIBUTIONS OF FOSSIL AND NON-FOSSIL CARBON SOURCES

ABSTRACT In order to better characterise carbonaceous components in atmospheric aerosols and to assess the contributions of fossil carbon (FC) and non-fossil carbon (NFC) sources and their seasonality in the Eastern Mediterranean, we collected fine (PM1.3) aerosols at a remote marine background site, the Finokalia Research Station, Crete, Greece, over a period of one-year. PM1.3 samples were analysed for elemental carbon (EC), organic carbon (OC), water-soluble OC (WSOC), and stable carbon isotope ratio (δ13CTC) and radiocarbon content (14CTC) (pMC) of total carbon (TC). All the parameters, i.e., PM1.3, δ13CTC and 14CTC showed a clear temporal pattern with higher values in summer and lower values in autumn. The 14CTC ranged from 54.7 to 99.1 pMC with an average of 74.5 pMC during the entire year. The FC content in TC (FCTC) was found to be slightly lower in winter and almost stable in other seasons, whereas the NFC contents (NFCTC) showed a clear seasonality with the highest level in summer followed by spring and the lowest level in winter. Based on these results together with the seasonal distributions of organic tracers, we found that biomass burning (BB) and soil dust are two major sources of the fine aerosols in winter. Although biogenic emissions of VOCs followed by subsequent secondary oxidation processes are significant in summer followed by spring and autumn, pollen is a significant contributor to TC in spring. This study showed that emissions from fossil fuel combustion are significant (25.5%) but minor compared to NFC sources in the eastern Mediterranean.

Regional differences in molecular characteristics of atmospheric water-soluble organic carbon over northern China: Comparison of remote, rural, and urban environments

Atmospheric water-soluble organic carbon (WSOC) is a critical component of airborne particulates. It significantly affects the Earth's energy balance, air quality, and human health. Despite its importance, the molecular composition and sources of WSOC remain unclear, particularly in non-urban areas. In this study, we collected total suspended particulate (TSP) samples from three sites in northern China: Erenhot (remote site), Zhangbei (rural site), and Jinan (urban site). The WSOC components were analyzed using high-performance liquid chromatography coupled with high-resolution mass spectrometry. The results showed that the formula numbers of identified compounds exhibited a decreasing trend of Jinan (2647) > Zhangbei (2046) > Erenhot (1399). Among the assigned formulas, CHO compounds were the most abundant category for all three sites, accounting for 33 %–38 % of the identified compounds, followed by the CHON compounds with contributions of 27 %–30 %. In the remote site of Erenhot, CHO compounds were dominated by oxidized unsaturated organic compounds, and CHON compounds were mainly low-oxygenated aliphatic compounds, suggesting a significant influence of primary emissions. In contrast, the urban site of Jinan showed higher contributions of CHO and CHON compounds with elevated oxidation degrees, indicating the influence of more extensive secondary oxidation processes. Atmospheric WSOC in Erenhot and Zhangbei had abundant reduced sulfur-containing species, likely from coal or diesel combustion, while that in Jinan was characterized by aliphatic organosulfates and nitrooxy-organosulfates, which are mainly associated with traffic emissions and biogenetic sources, respectively. These findings reveal significant differences in the molecular composition of WSOC in different atmospheric environments and improve our understanding of the chemical properties, potential sources, and transformations of organic aerosols.

Study on the secondary oxidation behavior and microscopic characteristics of oxidized coal gangue.

Spontaneous combustion of coal gangue (CG) hills has caused varieties of secondary disasters that seriously endanger the ecological environment of the world. The emission law of index gases and their oxidation kinetics during the secondary oxidation process of CG with different ranks of oxidation were studied by using the temperature programmed device and online mass spectrometer (MS). Fourier transform infrared spectroscopy (FTIR) was used to reveal the changes of the CG internal active functional groups. The results showed that the energy required for the combustion of CG with low rank of pre-oxidation was significantly lower than that of the raw sample. However, as the oxidation rank increased, due to amounts of volatile components were released in the process of oxidation reaction, the CG in the combustion process of the emission of index gases and its oxygen consumption rate gradually reduced; the rapid oxidation stage shifted to the direction of the high temperature. In this study, the risk of spontaneous combustion of CG after oxidation at 80℃ under 3% oxygen concentration was the strongest. The results of this paper are of great guiding significance for exploring the spontaneous combustion characteristics of CG hills and their prevention by traditional covering method.

Synthesis of acetyl ferulic 7‐hydroxyisoflavone ester and evaluating its antioxidant activity on improving fish oil thermal stability

SummaryAcetyl ferulic 7‐hydroxyisoflavone ester (AHE) was synthesized and its antioxidant capacity in vitro was evaluated by free radical scavenging assay and thermo‐oxidative stability analysis of fish oil in this study. The formation of primary and secondary oxidation products can be effectively inhibited by AHE, tert‐butylhydroxyquinone (TBHQ), ferulic acid and 7‐hydroxyisoflavone. The intensity of UV‐Vis absorption spectra increased significantly, whereas the intensity of fluorescence spectra decreased obviously with the deepening of oxidation degree of fish oil. AHE significantly alleviated the degradation of unsaturated fatty acids in fish oil. The results demonstrated that AHE was more effective than TBHQ, ferulic acid and 7‐hydroxyisoflavone in retarding the oxidative degradation of fish oil during high temperature storage (80 °C). Moreover, the formation of oxidation products in fish oil followed a first‐order kinetic model, and AHE effectively reduced reaction rate constant and delayed secondary lipid oxidation process. As a result, AHE is an effective antioxidant that can stabilise fish oil.

An experimental investigation of how coal's secondary oxidation process is impacted by primary oxidation temperature and ventilation

A worldwide calamity has resulted from spontaneous coal combustion, and actions such as opening enclosed fire areas and processing coal left in mines can ignite oxidized coal. Using a procedural temperature rise testing system, the impact of various primary oxidation temperatures and ventilation rates on secondary coal oxidation was examined in this research. The variation laws of the indicator gas, characteristic temperature, and exothermicity parameters were mainly analyzed, and the activation energy of each stage in the low-temperature oxidation process was calculated. The findings demonstrate that the secondary oxidation process's trend of sign gases (CO and C2H4) and exothermic characteristic characteristics of coal with temperature is unaffected by the primary oxidation temperature and ventilation. Increasing ventilation reduces the indicator gas concentration and the coal's exothermic characteristic parameters in the initial stages of low-temperature secondary oxidation, whereas it has the reverse effect in the later stages. Stage Ⅰ of the secondary low-temperature combustion procedure is significantly influenced by ventilation and the first oxidation temperature, but stages Ⅱ and III are only marginally affected. When the coal is secondarily oxidized at low temperatures, primary oxidation reduces the Ea of stage I, while increased ventilation raises the Ea of stage I. T1 (critical temperature) rises as the airflow rate rises, whereas T2 (dry cracking temperature) falls. The findings can provide theoretical guidance to open enclosed fire areas and process coal left in mines and other goaf operations and can further enrich the theory of preventing and controlling secondary coal oxidation.

Study on the thermal release characteristics and the correlation transformation mechanism of microscopic active groups of oxidized coal combustion in a deep mined-out area

With the normalization of deep mining, the risk of residual coal spontaneous combustion (CSC) in deeply mined areas has gradually increased. To investigate the thermal characteristics and microgroup transformation mechanisms during the secondary oxidation of deep-well oxidized coal, a deep-well oxidation process was simulated in a synchronous thermal analyzer, and the thermal parameters of the oxidized coal were tested. The correlated transformation pathways of microscopic active groups was studied by electron paramagnetic resonance (EPR) and in situ diffuse reflectance (in situ FTIR) experiments during the reoxidation of oxidized coal. The results showed that with increasing deep-well ambient temperature and oxidation temperature, the characteristic temperature of coal gradually decreased, exothermic heat release gradually increased, and active aliphatic structures and -OH, -CHO and other active functional groups gradually accumulated and became distributed more uniformly. When the thermal conditions and oxidation temperature were very high (> 160 °C), the active free radicals in the oxidized coal were rapidly consumed, resulting in a gradual decrease in the characteristic temperature and heat release during the secondary oxidation process, while the contents of peroxy and carboxyl groups continued to increase. In the slow oxidation stage of oxidized coal, methyl groups were mainly transformed with hydroxyl and peroxide groups (r > 0.96), and the associated oxidative consumption of -CHO and -COOH mainly occurred in the rapid oxidation stage (r > 0.99). Geminal diols and peroxy groups are important intermediates in the coal–oxygen composite reaction process. With an increase in the deep-well temperature and initial oxidation temperature, the reoxidation tendency and heat release capacity of residual coal in the goaf gradually increased, and the risk of CSC intensified. The research results provide a theoretical reference for the prevention and control of coal fires in deep mines and play an important role in guiding environmental management and gas emissions reduction measures in mining areas.

Effect of Secondary Oxidation of Pre-Oxidized Coal on Early Warning Value for Spontaneous Combustion of Coal

The indicative ability of a gas indicator for the spontaneous combustion of coal is affected by the secondary oxidation of oxidized coal, from old goafs, entering a new goaf through air leakages. This phenomenon can affect the accuracy of early warning systems regarding the spontaneous combustion of coal in a goaf. In this research, three kinds of coal were selected to carry out a spontaneous combustion simulation experiment in which a temperature-programmed experimental device was used to analyze the behavior of the index gas towards raw coal and oxidized coal, for which the latter was oxidized at 70 °C, 90 °C, 130 °C, and 150 °C. The results show that the chain alkane ratio in the secondary oxidation process and the trends of oxygen, CO, and C2H4 concentrations are the same as those in the primary oxidation process. On the other hand, the temperature at which C2H4 initially appears, during secondary oxidation, is lower than in primary oxidation. The CO produced in the early stage of secondary oxidation is greater than the CO produced, at the same temperature, in primary oxidation. In this regard, the usage of C2H4 concentration as an indicator with which to judge the occurrence of the spontaneous combustion of coal would allow for an earlier response. In the secondary oxidation process, the temperature of the extreme value of the alkene ratio appears higher than in primary oxidation. The presence of a higher pre-oxidation temperature and a higher proportion of secondary oxidation gas will affect an indicator’s judgement when the primary oxidation enters the severe oxidation stage. The gas produced by secondary oxidation will affect the early warning of the spontaneous combustion of coal in the coal mine goaf, which should be considered in the establishment of an early warning system.

Influence of Water Immersion Time on Re-Ignition Characteristics of High Temperature Oxidized Coal

ABSTRACT After a coal seam is mined, the oxidized coal left in its goaf is prone to water immersion, and spontaneous combustion accidents involving water-immersed coal may easily occur when mining the underlying coal seam. Using scanning electron microscopy and nitrogen adsorption experimental methods, the physical structure of high-temperature pre-oxidized water-immersed coal samples was characterized. By means of infrared spectroscopy, electron spin resonance (ESR) and simultaneous thermal analysis, the microscopic characteristics of the coal samples and the endothermic and exothermic characteristics of the oxidative combustion process were studied. The results showed that a specific pre-oxidation soaking time generated more oxidation pores in the coal sample, causing more water to become trapped in the pores and increasing the secondary oxidation heat absorption. High-temperature oxidation promoted the conversion of coal sample functional groups (FG) and free radical active sites, Water immersion led to the formation and loss of FG, and the longer the water immersion time was, the greater the loss. The larger average pore size of the pre-oxidized water-immersed coal sample provided more coal-oxygen contact sites, and the breaking of chemical bonds in the FG during the secondary oxidation process accelerated the heat release and promoted the oxidative re-ignition of the coal sample. The spontaneous combustion of water-immersed coal in the goaf can be prevented by controlling the high oxidation temperature and water immersion time.

Study on the Influence of the Mechanical Crushing Process on Low-Temperature Oxidation Characteristics of Coal Samples

ABSTRACT In order to study the influence of the mechanical crushing process on the low-temperature oxidation characteristics of coal, the programmed heating experiments of coal samples with different particle sizes were carried out using a programmed heating device. By comparing and analyzing the changes in CO and CO2 emission, cross-point temperature, heat release intensity, and apparent activation energy of coal samples with different particle sizes during temperature heating, the influence of particle sizes on the spontaneous combustion characteristics of coal samples was obtained. On the basis of the infrared spectrum experiment and ESR (electron paramagnetic resonance) experiment of coal samples with different particle sizes, the changes of functional groups and free radicals were further compared, and the deep-seated reasons that the mechanical crushing process affected the spontaneous combustion characteristics of coal were explored. The results showed that with the decrease in particle size, more alkyl side chains are dehydrogenated to produce alkyl radicals during mechanical crushing, and the alkyl radicals are oxidized with oxygen to form more oxygen-containing functional groups. These oxygen-containing functional groups can accelerate the low-temperature oxidation process of coal in the subsequent secondary low-temperature oxidation process, release more heat, and increase the heat release intensity. In the process of mechanical crushing, the coal sample not only changes in physical structure but also changes in chemical structure. With the decrease in particle size of coal samples, more CO and CO2 are produced in the process of low-temperature oxidation of coal, and the time to reach the cross-point temperature is advanced. However, the cross-point temperature and the apparent activation energy decreases, and the spontaneous combustion characteristics of coal are enhanced.

Effects of pre-oxidized temperature and pre-oxidized oxygen concentration on burning characteristics of pre-oxidized coal

The secondary oxidation of residual coal during re-mining in goaf will seriously endanger mine safety production. To investigate the influence of the formation process of PC(pre-oxidized coal) in goaf on the secondary oxidation of coal, This paper utilized the TG-DSC analysis method to study the burning characteristics of PC under different pre-oxidized temperatures and different pre-oxidized oxygen concentrations. The results showed that both PT(pre-oxidation temperature) and POC(pre-oxidation oxygen concentration) have effects on the burning process of oxidized coal, and there is an optimal POC and the best PT. Both PT and POC only have significant effects on the characteristic temperatures before ignition temperature, and fewer effects on the ignition temperature and the characteristic temperatures after ignition temperature, and thus PT and POC only have effects on the first three stages of the secondary oxidation process of PC, i.e., water evaporation and gas desorption stage, oxygen absorption stage of weight gain, and thermal decomposition stage. The effects of PT and POC are different from each characteristic temperature, thus the effects of PT and POC are different in the first three stages. In general, the secondary oxidation process of PC Y-18 %-100 is the most dangerous when re-mining the residual coal in the goaf. However, different pre-oxidized coals have different risks in different stages of the secondary oxidation process, because the types of active structures mainly involved in the coal-oxygen reaction in each stage are different, and the PT and POC during the formation of pre-oxidized coals will affect the number of active structures involved in the coal-oxygen reaction during the secondary oxidation of pre-oxidized coals. The DSC curves of PC at 300 °C showed no obvious plateau of heat uptake, which was because the too high PT would decompose the steady aromatic ring structures in the coal samples. The research results can be used as the theoretical basis for the re-mining of goaf, and ensure the safety of workers and the smooth progress of re-mining.

Development and characterization of active packaging films based on chitosan, plasticizer, and quercetin for repassed oil storage

Novel chitosan (Ch) films containing choline chloride and citric acid mixture as plasticizer (deep eutectic solvent, DES) and different amounts of quercetin (QUE) as antioxidant additive were prepared. Physicochemical and mechanical characteristics of the developed Ch/DES/QUE films were studied using FTIR, SEM, and AFM techniques. FTIR spectra revealed the possible interactions between all the components. The surface of the films was dense and rough. The addition of quercetin caused an increase in the tensile strength (TS) and Young's modulus, but significantly decreased the elongation at break. The films containing quercetin showed improved antioxidant activity in relation to Ch/DES film. Finally, the oxidation phenomena of rapeseed oils with and without chitosan films were evaluated as amounts of primary and secondary oxidation products and total oxidation index. The addition of Ch/DES films with quercetin to oil samples successfully retarded secondary lipid oxidation processes and improved its antioxidant activity under the accelerated storage condition.

Sulfide Variation in the Coeur Rochester Silver Deposit: Use of Geologic Block Modeling in the Prediction and Management of Mine Waste

Abstract A critical issue in mine waste management is the management and mitigation of acid rock drainage and metal leaching particularly from waste rock. This requires good understanding and characterization of materials most likely to generate acid pH waters and generate leachable metals and metalloids, as well as the presence of minerals most likely to neutralize acidic pH such as carbonates and certain silicates. For low-sulfidation epithermal deposits in silica-rich volcanic rocks, neutralization minerals are rare. Consequently, determination of acid generation is almost entirely a function of sulfide content of the rocks. By understanding the distribution of sulfide minerals within such a deposit, an initial mine waste management plan can be developed. The Rochester mine currently exploits a low-sulfidation epithermal gold-silver deposit and is located on the southern flank of the Humboldt Range in west-central Nevada. The Rochester mine is a conventional open-pit mining operation with cyanide heap leaching and Merrill Crowe processing. Silver and lesser gold mineralization occur associated with sulfide minerals hosted in Permian-Triassic Koipato Group rhyolitic units with extensive quartz-sericite-pyrite alteration. Gangue mineralogy of the deposit is dominated by slow or unreactive silicate minerals with little or no carbonate. Silver-bearing mineralization was controlled by primary hypogene sulfides and secondary supergene oxidation processes, and most of the mineralized material mined to date has been fully or partially oxidized. Oxidation mobilizes and depletes all forms of sulfur from primary sulfide minerals. Due to the low sulfate content and low content of neutralizing gangue phases, the waste rock classification can be based on total sulfur content. Based on the analysis of pulp samples collected from within the mine area, a sulfur block model was developed and compared to the results of standard acid-base accounting and net acid generation tests. This comparison demonstrates the benefit of the block model in identifying zones of potentially acid-generating material in the mined waste. Application of this information to mine planning has allowed more efficient management of acid-generating mine waste by allowing the operator to develop areas of the waste rock facility to receive the waste in a timely fashion. Such an approach is based on good mine geologic and mineralogical characterization and the use of a representative and comprehensive geologic block model.

Biomass burning plume chemistry: OH-radical-initiated oxidation of 3-penten-2-one and its main oxidation product 2-hydroxypropanal

Abstract. In order to enlarge our understanding of biomass burning plume chemistry, the OH-radical-initiated oxidation of 3-penten-2-one (3P2), identified in biomass burning emissions, and 2-hydroxypropanal (2HPr) was investigated at 298 ± 3 K and 990 ± 15 mbar in two atmospheric simulation chambers using long-path FTIR spectroscopy. The rate coefficient of 3P2 + OH was determined to be (6.2 ± 1.0) × 10−11 cm3 molec.−1 s−1 and the molar first-generation yields for acetaldehyde, methyl glyoxal, 2HPr, and the sum of peroxyacetyl nitrate (PAN) and CO2, used to determine the CH3C(O) radical yield, were 0.39 ± 0.07, 0.32 ± 0.08, 0.68 ± 0.27, and 0.56 ± 0.14, respectively, under conditions where the 3P2-derived peroxy radicals react solely with NO. The 2HPr + OH reaction was investigated using 3P2 + OH as a source of the α-hydroxyaldehyde adjusting the experimental conditions to shift the reaction system towards secondary oxidation processes. The rate coefficient was estimated to be (2.2 ± 0.6) × 10−11 cm3 molec.−1 s−1. Employing a simple chemical mechanism to analyse the temporal behaviour of the experiments, the further oxidation of 2HPr was shown to form methyl glyoxal, acetaldehyde, and CO2 with estimated yields of 0.27 ± 0.08, 0.73 ± 0.08, and 0.73 ± 0.08, respectively.

GC investigation of post-irradiation oxidation phenomena on polypropylene

Abstract The paper summarizes the results of research on gas products of polypropylene (PP) radiolysis. Particular attention was paid to the phenomena of post-radiation degradation of PP. The protective effect of selected aromatic compounds was investigated. The research was carried out both from the point of view of obtaining radiation-resistant PP varieties and the possibility of accelerating biodegradation phenomena, e.g., PP/cellulose composition. The phenomena of post-radiation chain oxidation of PP were investigated by gas chromatography (GC). The GC in the system used (packed column, thermal conductivity detector, argon – carrier gas) enables the determination of H2, O2, CO, and CH4 in one measurement. The samples were irradiated with electron beams (EBs) accelerated in accelerators: Elektronika 10/10 with a power of 10 kW and energy of 10 MeV and LAE 13/9 with a power of 9 kW and energy up to 13 MeV. In the tests, PP without stabilizing additives (obtained directly from the production line) and non-stabilized styrene were used. Radiolytic efficiency of hydrogen evolution allowed us to estimate the number of originally formed free radicals. The maintenance of the secondary oxidation processes was the loss of oxygen and the formation of oxidation products (CO, CH4). Attention is paid to the protective effect of aromatic compounds (polystyrene (PS), polyethylene terephthalate (PET), anthracene, fluoranthene, acenaphthene, pyrene, naphthalene) both at the stage of hydrogen atom separation and the secondary oxidation process. The examples of post-radiation oxidation of PP irradiated in cryogenic conditions (–196°C) are presented. All used aromatic compounds showed a protective effect in PP radiolysis. We suppose that this phenomenon is responsible for the charge transfer along the polymer chain from the ionization spurs to the aromatic compound. The protective ranges of PS in PP radiolysis were estimated for the variously prepared PP/PS type compositions from 6 mers to 28 mers.

Study on Spontaneous Combustion Characteristics of Coal Samples with Different Pre-oxidized Temperatures in Secondary Oxidation Process

ABSTRACT The paper used thermogravimetric experiments to study the spontaneous combustion characteristics of coal samples with different pre-oxidized temperatures during the secondary oxidation process and focused on the calculation of kinetic parameters during the oxygen-absorbing and weight-increasing stage. The results showed that the total reaction course of spontaneous combustion of raw coal and pre-oxidized coal were similar; the difference in pre-oxidized temperature only had a greater impact on the critical temperature and dry cracking temperature of the coal sample, and then had a greater impact on the water evaporation and desorption stage and the oxygen-absorbing and weight-increasing stage. And the oxygen-absorbing and weight-increasing stage had a more violent reaction than the water evaporation and desorption stage. In the oxygen-absorbing and weight-increasing stage, the difference of pre-oxidized temperature had little effect on the reaction mechanism of each coal sample. The reaction functions all followed the Jander equation, and the mechanism was three-dimensional diffusion. The energy of activation of pre-oxidized coal samples was smaller than that of raw coal, and decreased with the rise of pre-oxidized temperature. When the pre-oxidized temperature was less than 160°C, the pre-factor of the pre-oxidized coal was larger than that of the raw coal, and when the pre-oxidized temperature was greater than 160°C, the pre-exponential factor of the pre-oxidized coal was smaller than that of the raw coal. The research results can lay a foundation for the subsequent prediction of coal spontaneous combustion reaction process, determination of critical spontaneous combustion conditions and evaluation of inhibitory effect. At the same time, it can also be used as a reference and supplement for the existing research on coal oxidation kinetic parameters.

Secondary oxidation of crushed coal based on free radicals and active groups

The secondary oxidation of active groups was studied for crushed coals with various particle sizes. Then, free radicals of these crushed coals were comparatively analyzed after primary and secondary oxidation. The secondary oxidation of active structures on the coal surface was studied by combining the theories of free radicals and functional groups. The coal oxidation reactivity was stronger in Particle 5#. Secondary oxidation had a stronger effect on the reactivity of high-rank coal. A relatively stable aliphatic chain structure was formed during the secondary oxidation of low-rank Coal 1#. The aliphatic hydrocarbon structure was relatively active in high-rank Coals 2# and 3#. Primary oxidation can improve the oxidizability of the aliphatic hydrocarbon structure and facilitate its secondary oxidation process. The OH group in Coal 1# possesses stronger oxidation reactivity and was consumed rapidly during secondary oxidation. In contrast, the consumption and generation rate of the OH group tended to reach a balance in Coal 2# and Coal 3#. CO and CO groups in Coal 1# experienced relatively violent secondary oxidation. The two groups in Coal 2# and Coal 3# experienced relatively gentle secondary oxidation.

1H–NMR fingerprinting and supervised pattern recognition to evaluate the stability of virgin olive oil during storage

Metabolomic fingerprinting of virgin olive oil (VOO) by 1H NMR spectroscopy was used to study its stability during storage simulating normal shelf life conditions during its commercialization. A representative set of VOOs covering the full range of possible chemical compositions were exposed to light (500 lux for 12 h/day) at 25 °C for 12 months or stored in the dark at 25 °C, 30 °C and 35 °C for 24 months. Multivariate data analysis of the 1H NMR spectra of the oil samples provided classification models to evaluate VOO freshness and to verify the light exposure of the VOO during storage, as well as regression models to determine VOO storage time and tentatively the best before date of a fresh VOO. These predictive models disclosed the chemical compounds responsible for the compositional changes in VOO due to hydrolytic and oxidative degradation taking place during its storage, and confirmed that light and increasing temperature enhance these processes. The presence of characteristic resonances of hydroperoxides (primary oxidation products) and the decrease of 1H signals assigned to phenolic compounds, mainly secoiridoid derivatives, and other minor compounds such as fatty acids, squalene and native (E)-2-hexenal present in fresh VOO revealed its oxidative degradation. Further, the emergence of low intensity 1H signals of saturated aldehydes meant that the secondary oxidation process has started at a low rate and yield. Moreover, the decrease of the 1H signals of triacylglycerides and sn-1,2-diacylglycerides, and the increase of sn-1,3-diacylglycerides indicated that hydrolytic degradation of VOO and diacylglyceride isomerisation was occurring. 1H NMR fingerprint of VOO together with pattern recognition techniques afford relevant information to assess the quality of VOOs taking into consideration legal, sensory and health-promoting aspects.

Effect of particle size and low-temperature secondary oxidation on the active groups in coal structures

To analyze the secondary oxidation of the active structures of pulverized coal and reduce risks of coal spontaneous combustion, free radical theory and functional group analysis were combined to study the effects of particle size and oxidation temperature on the active structure of coal molecules. This process was based on electron paramagnetic resonance (EPR) and Fourier-transform infrared (FTIR) technology. The results show that the reduction in pulverized coal particle size can enhance the secondary oxidation activity of coal and that the reactivity is the strongest when the particle size is 0.074−0 mm. The smaller the coal particle size is, the shorter the aliphatic side chain is after secondary oxidation. The reaction in which the side chain breaks to form a stable chain structure is also more intense. A smaller coal particle size also makes it easier to produce −OH after secondary oxidation, resulting in a large increase in the Average A (−OH) in the Coal 1# and Coal 3# at the minimum particle size range of 0.074−0 mm. The −C=O and −C−O− in Coal 1# with a lower metamorphic grade are greatly affected by temperature and particle size, and the consumption of −C=O during oxidation plays a dominant role in the secondary oxidation process. The −C=O and −C−O− in Coal 2# and Coal 3# are less affected by temperature and more affected by particle size, and −C−O− is the main group driving the secondary oxidation reaction.

Volcano-like hierarchical superhydrophobic surface synthesized via facile one-step secondary anodic oxidation

Superhydrophobic surface has been extensively applied in the field of self-cleaning and corrosion prevention, and the common preparation route of the superhydrophobic surface involves the construction of rough structure and modification with low-surface-energy regents in multistep process. Herein, a facile one-step method was proposed to fabricate the superhydrophobic surface with the simultaneous construction and modification of hierarchical microstructure and surface, the volcano-like anodic aluminium oxide (AAO) -based superhydrophobic surfaces with controllable roughness were synthesized via secondary anodic oxidation (SAO) process of AAO film in an organic–inorganic sol–gel system. During the SAO process, the perfluorooctyl triethoxysilane, which covalently bonded onto the surface, resulted in the inhomogeneous distribution of surface free energy and heterogeneous generation of volcano-like structure. The hydrophobic ability was enhanced by the rough hierarchical micro-/nanostructure with low surface energy, and the TiO2/PFOTS-AAO-15 exhibited the optimal water repellence with a WCA of ~154°, self-cleaning performance and anticorrosion property in corrosive medium. This convenient method is anticipated to unlock various superhydrophobic surfaces on different substrates in the practical fields of self-cleaning and anticorrosion.

CAICE Studies: Insights from a Decade of Ocean-Atmosphere Experiments in the Laboratory.

Ocean-atmosphere interactions control the composition of the atmosphere, hydrological cycle, and temperature of our planet and affect human and ecosystem health. Our understanding of the impact of ocean emissions on atmospheric chemistry and climate is limited relative to terrestrial systems, despite the fact that oceans cover the majority (71%) of the Earth. As a result, the impact of marine aerosols on clouds represents one of the largest uncertainties in our understanding of climate, which is limiting our ability to accurately predict the future temperatures of our planet. The emission of gases and particles from the ocean surface constitutes an important chemical link between the ocean and atmosphere and is mediated by marine biological, physical, and chemical processes. It is challenging to isolate the role of biological ocean processes on atmospheric chemistry in the real world, which contains a mixture of terrestrial and anthropogenic emissions. One decade ago, the NSF Center for Aerosol Impacts on Chemistry of the Environment (CAICE) took a unique ocean-in-the-laboratory approach to study the factors controlling the chemical composition of marine aerosols and their effects on clouds and climate. CAICE studies have demonstrated that the complex interplay of phytoplankton, bacteria, and viruses exerts significant control over sea spray aerosol composition and the production of volatile organic compounds. In addition, CAICE experiments have explored the physical production mechanisms and their impact on the properties of marine cloud condensation nuclei and ice nucleating particles, thus shedding light on connections between the oceans and cloud formation. As these ocean-in-the-laboratory experiments become more sophisticated, they allow for further exploration of the complexity of the processes that control atmospheric emissions from the ocean, as well as incorporating the effects of atmospheric aging and secondary oxidation processes. In the face of unprecedented global climate change, these results provide key insights into how our oceans and atmosphere are responding to human-induced changes to our planet.This Account presents results from a decade of research by chemists in the NSF Center for Aerosol Impacts on Chemistry of the Environment. The mission of CAICE involves taking a multidisciplinary approach to transform the ability to accurately predict the impact of marine aerosols on our environment by bringing the full real-world chemical complexity of the ocean and atmosphere into the laboratory. Toward this end, CAICE has successfully advanced the study of the ocean-atmosphere system under controlled laboratory settings through the stepwise simulation of physical production mechanisms and incorporation of marine microorganisms, building to systems that replicate real-world chemical complexity. This powerful approach has already made substantial progress in advancing our understanding of how ocean biology and physical processes affect the composition of nascent sea spray aerosol (SSA), as well as yielded insights that help explain longstanding discrepancies in field observations in the marine environment. CAICE research is now using laboratory studies to assess how real-world complexity, such as warming temperatures, ocean acidification, wind speed, biology, and anthropogenic perturbations, impacts the evolution of sea spray aerosol properties, as well as shapes the composition of the marine atmosphere.