Enhancing the combustion of nAl with AlF3 coating: gas-solid reaction mechanism for reducing combustion agglomeration of Al powder.

The combustion agglomeration of nano-aluminum (nAl) powder leads to incomplete combustion, which seriously hinders its application as metal fuel. In this work, nAl@AlF3 composites were produced by coating nAl with AlF3via a facile chemical deposition method. TEM and SEM analyses indicated that the AlF3 layer was evenly coated on the surface of nAl with a thickness of 4.6-9.1 nm, thereby varying the quantity of AlF3 applied. Experimental results from combustion indicated that the prepared nAl@AlF3 composites exhibit superior combustion efficiency, a higher combustion rate, and reduced combustion agglomeration as compared to raw nAl. Contrary to the widely accepted explanation that volatilization of AlF3 hinders Al combustion agglomeration, we proved that the gas-solid reaction between nAl and AlF3 plays an important role in inhibiting the sintering of nAl particles produced. The gaseous intermediate (i.e., AlOF and HF) released from the hydrolysis of AlF3 could reduce the diffusion barrier of Al2O3 to facilitate the reaction of Al core, which enhances the combustion reaction kinetics. More importantly, these gaseous products actively participate in the reaction cycle to continuously exert their catalytic effects.

Photosensitized Transformation of Peroxymonosulfate in Dissolved Organic Matter Solutions under Simulated Solar Irradiation.

Sulfate radical (SO4•-)-mediated advanced oxidation processes via peroxymonosulfate (PMS) activation have been extensively investigated. However, the phototransformation of PMS in sunlit dissolved organic matter (DOM) solution has not been previously examined. For the first time, the photosensitized transformation of PMS in DOM-enriched solutions under simulated solar irradiation was observed. The generation of reactive species, including 1O2, SO4•-, and •OH, was confirmed by electron paramagnetic resonance and quantified by chemical probes. SO4•- was the primary reactive species generated via the reaction of excited triplet DOM (3DOM*) with PMS. 3DOM* acted as a reactive reductant and was quickly oxidized by PMS, with an estimated reaction rate constant of (4.09 ± 0.21) × 108 M-1 s-1. Compared to 3DOM*, one-electron-reducing DOM (DOM•-) was a minor contributor to the photosensitized transformation of PMS, and the contribution of DOM•- relied on the phenolic constituents. In addition, a series of different types of DOM, including terrestrial DOM, autochthonous DOM, and effluent organic matter and its fractions, were employed to examine the photosensitized transformation kinetics of PMS. Overall, the photosensitized transformation of PMS by irradiated DOM could be a useful and economical approach to generate SO4•- under environmentally relevant conditions.

Microheterogeneous Distribution of Hydroxyl Radicals in Illuminated Dissolved Organic Matter Solutions.

Hydroxyl radicals (•OH) are important reactive species that are photochemically generated through solar irradiation of chromophoric dissolved organic matter (CDOM) in surface waters. However, the spatial distribution within the complex three-dimensional structure of CDOM has not been examined. In this study, we used a series of hydrophobic chlorinated paraffins as chemical probes to elucidate the microheterogeneous distribution of •OH in illuminated CDOM solutions. The steady-state concentration of •OH inside the CDOM microphase is 210 ± 31-fold higher than the concentration in the aqueous phase. Our results suggest that the most photochemically generated •OH are confined into the CDOM microphase. Thus, illuminated CDOM behaves as a natural microreactor for •OH-based oxidations. By including intra-CDOM •OH, the quantum yield of •OH for CDOM solutions was estimated to be 2.2 ± 0.5 × 10-3, which is 2 orders of magnitude greater than previously thought. The elevated concentrations of photogenerated •OH within the CDOM microphase may improve the understanding of hydrophobic pollutant degradation in aqueous environments. Moreover, our results also suggest that •OH oxidation may play more important roles in the phototransformation of CDOM than previously expected.

Triplet Photochemistry of Dissolved Black Carbon and Its Effects on the Photochemical Formation of Reactive Oxygen Species.

Dissolved black carbon (DBC) is an important component of dissolved organic matter pool; however, its photochemical properties are not fully understood. In this study, we determined the excited triplet-state quantum yields of DBC (3DBC*) and 1O2 quantum yields (Φ1O2) of six diverse DBCs using sorbic alcohol, 2,4,6-trimethylphenol (TMP), and furfuryl alcohol and compared the results with quantum yields of reference natural organic matters (NOMs). The average Φ1O2 of six DBCs (4.2 ± 1.5%) was greater than that of terrestrial NOM (2.4 ± 0.3%) and comparable to autochthonous NOM (5.3 ± 0.2%). Using TMP as a probe for oxidizing triplets, DBC presented significantly higher apparent quantum yield coefficients for degrading TMP (fTMP) than the reference NOM, reflecting that the fTMP values of low-energy 3DBC* were approximately 12-fold greater than those of low-energy 3NOM*. The differences in the fTMP and Φ1O2 trends among the DBCs indicated that the 3DBC* responsible for these reactions may be from different sources. In addition, DBC was much more effective than NOM, on a carbon-normalized basis, during photodegradation of pharmaceutically active compounds. This result confirms that the presence of DBC can accelerate the photodegradation of contaminants that are susceptible to one-electron oxidation by triplets.

Kinetic Consideration of Photochemical Formation and Decay of Superoxide Radical in Dissolved Organic Matter Solutions.

The photochemical formation and decay rates of superoxide radical ions (O2•-) in irradiated dissolved organic matter (DOM) solutions were directly determined by the chemiluminescent method. Under irradiation, uncatalyzed and catalyzed O2•- dismutation account for ∼25% of the total O2•- degradation in air-saturated DOM solutions. Light-induced O2•- loss, which does not produce H2O2, was observed. Both the O2•- photochemical formation and light-induced loss rates are positively correlated with the electron-donating capacities of the DOM, suggesting that phenolic moieties play a dual role in the photochemical behavior of O2•-. In air-saturated conditions, the O2•- quantum yields of 12 DOM solutions varied in a narrow range, from 1.8 to 3.3‰, and the average was (2.4 ± 0.5)‰. The quantum yield of O2•- nonlinearly increased with increasing dissolved oxygen concentration. Therefore, the quantum yield of one-electron reducing intermediates, the precursor of O2•-, was calculated as (5.0 ± 0.4)‰. High-energy triplets (3DOM*, ET > 200 kJ mol-1) and 1O2 quenching experiments indicate that 3DOM* and 1O2 play minor roles in O2•- production. These results are useful for predicting the photochemical formation and decay of O2•- in sunlit surface waters.

Effects of Thermal Damage on Impact Response Characteristics of High-Energy Propellants.

Thermal damage due to microstructure changes will occur in propellants under thermal stimulation. It can significantly affect the sensitization, combustion, and other properties of the propellant, which, in turn, affects the impact safety of the solid propellant rocket engine. A new component which uniformly heats the sample was designed to conduct the Lagrange test and EFP impact test at different temperatures. The thermal decomposition and damage characteristics of the propellant during the heating process were quantitatively analyzed. Additionally, the effects of ambient temperature on impact initiation and detonation growth of the high-energy propellant were elucidated at a mesoscopic level. The results showed that the porosity of the specimen increased by 0.89% under the thermomechanical mechanism, which was mainly characterized by interfacial de-bonding between the AP and the binder. The increase in thermal damage changed the hot spot reaction rate and significantly affected the growth process of propellant impact initiation. A method was proposed to systematically calibrate the reaction rate model for the propellant at different temperatures. The theoretical model parameters of the high-energy propellant at two typical temperatures were calibrated in this way. The critical shell thicknesses computed using LS-DYNA, which, for 20 and 70 °C, were obtained as 15 and 20 mm, respectively.

Interaction Mechanism of Composite Propellant Components under Heating Conditions.

To examine the interactions between two binder systems-hydroxyl-terminated polybutadiene (HTPB) and hydroxyl-terminated block copolyether prepolymer (HTPE)-as well as between these binders and ammonium perchlorate (AP) at various temperatures for their susceptibility to varying degrees of thermal damage treatment, the thermal characteristics and combustion interactions of the HTPB and HTPE binder systems, HTPB/AP and HTPE/AP mixtures, and HTPB/AP/Al and HTPE/AP/Al propellants were studied. The results showed that the first and second weight loss decomposition peak temperatures of the HTPB binder were, respectively, 85.34 and 55.74 °C higher than the HTPE binder. The HTPE binder decomposed more easily than the HTPB binder. The microstructure showed that the HTPB binder became brittle and cracked when heated, while the HTPE binder liquefied when heated. The combustion characteristic index, S, and the difference between calculated and experimental mass damage, ΔW, indicated that the components interacted. The original S index of the HTPB/AP mixture was 3.34 × 10-8; S first decreased and then increased to 4.24 × 10-8 with the sampling temperature. Its combustion was initially mild, then intensified. The original S index of the HTPE/AP mixture was 3.78 × 10-8; S increased and then decreased to 2.78 × 10-8 with the increasing sampling temperature. Its combustion was initially rapid, then slowed. Under high-temperature conditions, the HTPB/AP/Al propellants combusted more intensely than the HTPE/AP/Al propellants, and its components interacted more strongly. A heated HTPE/AP mixture acted as a barrier, reducing the responsiveness of solid propellants.

Tuning the Reactivity of Perfluoropolyether-Functionalized Aluminum Nanoparticles by the Reaction Interface Fuel-Oxidizer Ratio.

To deepen the oxidation depth and promote the exothermic reaction of aluminum nanoparticles (Al NPs), this work constructed perfluoropolyether-functionalized Al NPs by using a facile fabrication method. It was determined that perfluoropolyether (PFPE) was uniformly distributed on the surface of the Al NPs with no obvious agglomeration by micro-structure analysis. Thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), microcomputer automatic calorimeter (MAC), and combustion and ignition experiments were performed for varying percentages of PFPE blended with Al NPs to examine the reaction kinetics and combustion performance. It was revealed that the oxidation mechanism of PFPE-functionalized Al NPs at a slow heating rate was regulated by the reaction interface Fuel-Oxidizer ratio. Due to the enlarged Fuel-Oxidizer contact surface area, fluorine atoms could adequately decompose the inert alumina shell surrounding the Al NPs, optimizing the combustion process of Al NPs. The analytical X-ray diffraction (XRD) pattern results confirmed the existence of aluminum trifluoride in combustion products, providing insights into the oxidation mechanism of Al NPs. The obtained results indicated that PFPE participated in the oxidation of Al NPs and improved the overall reactivity of Al NPs.

Direct degradation of methylene blue by unactivated peroxymonosulfate: reaction parameters, kinetics, and mechanism.

Advanced oxidation processes (AOPs) are efficient methods for water purification. However, there are few studies on using peroxymonosulfate (PMS) to remove pollutants directly. In this study, about 76% of methylene blue (MB) was removed by PMS directly within 180 min through a non-radical pathway, verified by scavenging tests, electron paramagnetic resonance and kinetic calculations. Additionally, the effects of PMS dosage, MB concentration, temperature, initial pH and competitive anions were determined. High PMS dosage, temperature and pH promoted MB degradation (from 76 to 98%) while MB concentration showed no effect on MB removal. Besides, MB degradation followed pseudo-first-order kinetic with rate constants of 0.0082 to 0.3912 min-1. The second-order rate constant for PMS reaction with MB was 0.08 M-1 s-1 at pH 3-6, but increased dramatically to 4.68 M-1 s-1 at pH 10.50. Chlorine could be catalysed by PMS at high concentration Cl- and degradation efficiency reached 98% within 90 min. High concentration of bicarbonate accelerated MB removal due to the high pH value while humic acid showed a marginal effect on MB degradation. Furthermore, TOC removal rate of MB in the presence of chloride reached 45%, whereas PMS alone caused almost no mineralisation. This study provides new insights into pollutant removal and an additional strategy for water purification.

Degradation of tetrabromobisphenol A by ferrate(VI)-CaSO3 process: Kinetics, products, and impacts on following disinfection by-products formation.

Tetrabromobisphenol A (TBBPA) is one of the most widely applied brominated flame retardants and has been widely detected in water environment, which might pose risks of brominated disinfection by-products formation in water treatment system. Ferrate(VI)-CaSO3 (Fe(VI)-CaSO3) system could effectively degrade TBBPA at pH 7.0-9.0 but the decomposition rate of TBBPA dropped with increasing pH. The presence of 0.5 mg C/L humic acid (HA) had negligible impact on TBBPA removal, but the removal of TBBPA decreased to ~87% and 80% at pH 7.0 and 8.0, respectively, in the presence of 5.0 mg C/L HA. The transformation products of TBBPA detected in Fe(VI)-CaSO3 process revealed that TBBPA degradation mainly proceeded via electron abstraction, debromination, and ring-opening pathways and Br- was released. In the presence of TBBPA, Fe(VI)-CaSO3 pre-oxidation decreased the generation of all determined DBPs during chlorination at pH 8.0 but it lessened the generation of some DBPs and slightly increased the formation of the other DBPs at pH 7.0. The toxic risk analysis showed that Fe(VI)-CaSO3 pre-oxidation of TBBPA could reduce the toxic risk of DBPs in both synthetic water and natural water at pH 8.0, indicating that Fe(VI)-CaSO3 process has the potential to be applied in practical water treatment.

Phototransformation of an emerging cyanotoxin (Aerucyclamide A) in simulated natural waters.

Aerucyclamide A (ACA) is an emerging cyanopeptide toxin produced by cyanobacteria, and its transformation pathway has rarely been reported. In the present study, ACA was purified from cyanobacterial extracts, and photodegradation processes were investigated in dissolved organic matter (DOM) solutions. Under simulated solar irradiation, the photodegradation of ACA was dominated by •OH oxidation, accounting for ~72% of the indirect photodegradation. The bimolecular reaction rate constant of ACA with •OH was (6.4 ± 0.2) × 109M - 1s - 1. Our results indicated that the major reactive sites of ACA toward •OH are thiazoline and thiazole moieties. Product analysis via high-resolution mass spectrometry suggested that hydrogen abstraction and gradual hydroxylation are the main photodegradation pathways. The acute toxicity assessment indicate that the products generated in photolysis process did not show any measurable toxicity to Thamnocephalus platyurus. Photodegradation experiments with various DOM-phycocyanin mixtures demonstrated that the half-life of ACA is much longer than that of microcystin-LR.

Development of fluorescence surrogates to predict the ferrate(VI) oxidation of pharmaceuticals in wastewater effluents.

The removal of pharmaceuticals from wastewater effluents is an emerging concern for environmental scientists and engineers. Ferrate(VI) (FeVIO42-, FeVI) is a promising oxidant and the removal of pharmaceuticals from wastewater effluents has been investigated in this study. Firstly, FeVI oxidation of selected pharmaceuticals was examined by determining the apparent second-order rate constants (kapp) in buffer solutions as a function of pH (5.0-9.5). At pH 8.0, kapp of cimetidine, famotidine, nalidixic acid, ronidazole, dimetridazole, tinidazole, and caffeine are (1.6 ± 0.2)×103, (7.8 ± 0.3)×102, 2.6 ± 0.4, 1.7 ± 0.1, 0.9 ± 0.3, 0.2 ± 0.1, and < 0.1 M-1 s-1, respectively. However, kapp could not be directly employed to predict the removal of pharmaceuticals in the effluents due to the inhibited or enhanced effects of effluent organic matters (EfOM). Therefore, an alternative approach of spectroscopic surrogates was investigated since fluorophore was co-degraded with pharmaceuticals in the wastewater effluents. Particularly, the humic-like fluorescent peak correlated well with the pharmaceutical attenuation. The relationship of the reduction of fluorescence and the removal of pharmaceuticals could be described through a universal equation: [Formula: see text] . The practical utility of the fluorescence surrogate was validated by applying to field samples. Monitoring the changes of the fluorescence surrogate provides a promising, rapid, and inexpensive method for estimating the degradation of pharmaceuticals during FeVI treatment of wastewater effluents.

Development of an ammonium chloride-enhanced thermal-assisted-ESI LC-HRMS method for the characterization of chlorinated paraffins.

Simultaneous quantification of short-, medium-, and long-chain chlorinated paraffins (CPs) in environmental matrices is challenging and has received much attention from environmental chemists. In this study, ammonium-chloride-enhanced liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) was developed for the first time to quantify CPs in sediments and aqueous samples. Three ionization sources, including atmospheric pressure chemical ionization (APCI), electrospray ionization (ESI), and thermal-assisted-ESI, were employed to examine the performance of ammonium chloride as the chloride ion supply reagent in comparison with traditional chloride ion supply reagent, dichloromethane. Ammonium chloride can be easily used with reversed-phase liquid chromatography (LC), whereas dichloromethane is not compatible with aqueous LC mobile phase. Furthermore, other anion-supply reagents, such as ammonium formate, ammonium acetate, and ammonium bromide, were also tested. It was concluded that the adducts of the CPs with the anions were reversible and could partially dissociate into deprotonated CP ions. The yield of deprotonated CP ions was associated with the gas-phase basicity of the deprotonated CP ions and the corresponding anions. Furthermore, collision-induced dissociation curves were drawn to quantify the stability of anionic CP adducts. The ammonium-chloride-enhanced LC-HRMS was further employed for identifying CPs in sediment samples and coupled with an online SPE method for detecting CPs in aqueous samples. This study may significantly contribute to the qualification and quantification of CPs in environmental matrices.

A Rapid Fenton treatment of bio-treated dyeing and finishing wastewater at second-scale intervals: kinetics by stopped-flow technique and application in a full-scale plant.

A rapid Fenton treatment at second-scale intervals was investigated for further removal of organic compounds in the effluent of bio-treated dyeing and finishing wastewater (BDFW). The decolorization kinetics was studied using a stopped-flow spectrophotometer (SFS) at second-scale intervals. A combined first-order model was found to fit well for the decrease of both methylene blue and rhodamine B in SFS as well as SCOD (soluble chemical oxygen demand) and DOC (dissolved organic carbon) in real BDFW in batch test during Fenton oxidation. A full-scale plant with treatment capacity of 400,000 m3·d-1 was designed and has been run continuously based on the results of the stopped-flow study to treat the effluent of BDFW using Fenton oxidation in 16 pipeline reactors, each with a volume of 6.9 m3 and 24 s of reaction time since 2014. The COD, SCOD and DOC decreased from 140, 110 and 35 mg·L-1 to 77, 71 and 26 mg·L-1 respectively, which can meet the latest strict discharge limitations. The natural fluorescent substances detected in the BDFW were completely removed. The main organic pollutants in the BDFW can be significantly reduced using both gas chromatography-mass spectrometry and ultrahigh-performance liquid chromatography-hybrid quadrupole time-of-flight mass spectrometry. The rapid Fenton reaction applied in pipeline reactors at second intervals has several advantages over the conventional Fenton's process such as much shorter reaction time at second scale intervals, no need to build extra pH adjustment or reaction tanks, simple operation, low capital cost, etc.

Photochemical oxidation of PPCPs using a combination of solar irradiation and free available chlorine.

The degradation of pharmaceuticals and personal care products (PPCPs) by using solar photolysis in the presence of free available chlorine (FAC) was investigated in simulated drinking water. The combination of free available chlorine and sunlight irradiation dramatically accelerated the degradation of all the contaminants tested through the generation of hydroxyl radicals, reactive chlorine species (RCS) and ozone. Contaminants containing electron-donating moieties degraded quickly and were preferentially degraded by RCS and/or HO oxidation. Primidone, ibuprofen and atrazine, which contain electron-withdrawing moieties, were mainly degraded by HO. Trace amounts of O3 contributed greatly to carbamazepine's degradation. Degradation of PPCPs was accelerated in oxygenated solutions. Increasing chlorine concentrations barely enhanced removal of PPCPs bearing electron-withdrawing moieties. Higher pH generally decreased the degradation rate constants along with reduced levels of HO and Cl, but diclofenac, gemfibrozil, caffeine and carbamazepine had peak degradation rate constants at pH 7-8. The cytotoxicity using Chinese hamster ovary (CHO) cell did not show significant enhancement in solar/FAC treated water. Combining chlorination with sunlight may provide a simple and energy-efficient approach for improving the removal of organic contaminants during water treatment.

Fenton treatment of bio-treated fermentation-based pharmaceutical wastewater: removal and conversion of organic pollutants as well as estimation of operational costs.

The Fenton process is used as a tertiary treatment to remove organic pollutants from the effluent of bio-treated pharmaceutical wastewater (EBPW). The optimal and most appropriate Fenton conditions were determined by an orthogonal array test and single-factor experiments. The removal of chemical oxygen demand (COD) was influenced by the following factors in a descending order: H2O2/Fe(II) molar ratio > H2O2 dosage > reaction time. Under the most appropriate Fenton conditions (H2O2/Fe(II) molar ratio of 1:1, H2O2 dosage of 120 mg L-1 and reaction time of 10 min), the COD and dissolved organic carbon (DOC) were removed with efficiencies of 62 and 53%, respectively, which met the national discharge standard (GB 21903-2008) for the Lake Tai Basin, China. However, the Fenton treatment was inadequate for removal of N compounds, and the removal of organic nitrogen led to an increment in N-NH3 from 3.28 to 19.71 mg L-1. Proteins and polysaccharides were completely removed, and humic acids (HAs) were partly removed with an efficiency of 55%. Three-dimensional excitation/emission matrix spectra (3DEEMs) indicated complete removal of fulvic acid-like substances and 90% reduction in the florescence intensity of humic acid-like substances. Organic pollutants with molecular weights (MW) > 10 kDa were completely removed, MW 5-10 kDa were degraded into smaller MW ones, and some low molecular weight acids (MW 0.1-1 kDa) were mineralized during the Fenton process. Some species, including pharmaceutical intermediates and solvents were detected by gas chromatography-mass spectrometry (GC-MS). The operational costs of the Fenton's treatment were estimated to be 0.58 yuan RMB/m3 EBPW based on reagent usage and iron sludge treatment and disposal.

Pilot-scale study on catalytic ozonation of bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst.

A pilot scale reactor with an effective volume of 2.93 m3 was built in-situ and run in both batch and continuous modes to investigate the removal for organic pollutants in bio-treated dyeing and finishing wastewater by heterogeneous catalytic ozonation under neutral pH with waste iron shavings as a catalyst. Experimental results showed that both running modes were able to reduce the chemical oxygen demand (COD) from 132-148 mg/L to a level below the discharge criteria (<80 mg/L) within 15-30 mins under several conditions. Specifically, significantly organic removal was observed with COD, soluble COD (sCOD) and dissolved organic carbon (DOC) decreased from the initial 165, 93 and 76 mg/L to 54, 28 and 16 mg/L respectively, when treated by 10.2 g-O3/min of ozone dosage at a hydraulic retention time of 30 mins under continuous mode. 80% proteins and 85% polysaccharides were removed with a decrease in their contribution to sCOD from 69% to 43%. Mineralization as well as conversion of high molecular organic compounds was observed through Gas Chromatography-Mass Spectrometer (GC-MS) & Liquid Chromatography-Mass Spectrometer (LC-MS) analysis, which led to a decrease of inhibitory effect from 29% to 25%, suggesting a reduction in the acute toxicity.

Microbial nitrate removal by waste iron shavings from the biological and catalytic ozonation treated dyeing and finishing wastewater.

The concentration of total nitrogen (TN) (between 40 and 60 mg/L, mainly nitrate) in the biological and catalytic ozonation treated dyeing and finishing wastewater needs to be reduced before discharge. The present study investigated the feasibility of using waste iron shavings as electron donor for nitrogen removal by biological denitrification. Two anoxic sequencing batch reactors (AnSBR) were continuously operated for more than 100 days. The results showed that the TN removal efficiency increased from 12% in the control reactor (AnSBR-C) to 20% in the reactor with waste iron shavings (AnSBR-Fe). The TN removal was mainly achieved by the reduction of nitrate by heterotrophic denitrification and autotrophic denitrification for AnSBR-Fe. The residual COD (38.4 mg/L) in the effluent of AnSBR-Fe was higher than that (22 mg/L) in the effluent of AnSBR-C, which could be due to that the bacteria preferred to use iron instead of the recalcitrant organics that present in the wastewater. Furthermore, 3DEEM, UHPLC-QTOF and GC-MS analysis were used to characterize the organics in the wastewater, and the results showed that the addition of waste iron shavings affected the degradation of organics during the biological denitrification process.