Modulating the Electronic Structures of Pt on Pt/TiO2 Catalyst for Boosting Toluene Oxidation.

Surface hydroxyl groups commonly exist on the catalyst and present a significant role in the catalytic reaction. Considering the lack of systematical researches on the effect of the surface hydroxyl group on reactant molecule activation, the PtOx/TiO2 and PtOx-y(OH)y/TiO2 catalysts were constructed and studied for a comprehensive understanding of the roles of the surface hydroxyl group in the oxidation of volatiles organic compounds. The PtOx/TiO2 formed by a simple treatment with nitric acid presented greatly enhanced activity for toluene oxidation in which the turnover frequency of toluene oxidation on PtOx/TiO2 was around 14 times as high as that on PtOx-y(OH)y/TiO2. Experimental and theoretical results indicated that adsorption/activation of toluene and reactivity of oxygen atom on the catalyst determined the toluene oxidation on the catalyst. The removal of surface hydroxyl groups on PtOx promoted strong electronic coupling of the Pt 5d orbital in PtOx and C 2p orbital in toluene, facilitating the electron transfers from toluene to PtOx and subsequently the adsorption/activation of toluene. Additionally, the weak Pt-O bond promoted the activation of surface lattice oxygen, accelerating the deep oxidation of activated toluene. This study clarifies the inhibiting effect of surface hydroxyl groups on PtOx in toluene oxidation, providing a further understanding of hydrocarbon oxidation.

Highly efficient molecular film for inhibiting volatilization of hazardous nitric acid.

Nitric acid, an important basic chemical raw material, plays an important role in promoting the development of national economy. However, such liquid hazardous chemicals are easy to cause accidental leakage during production, transportation, storage and use. The high concentration and corrosive toxic gas generated from decomposition shows tremendous harm to the surrounding environment and human life safety. Therefore, how to inhibit the volatilization of nitric acid and effectively control and block the generation of the toxic gas in the first time are the key to deal with the nitric acid leakage accident. Herein, a new method of molecular film obstruction is proposed to inhibit the nitric acid volatilization. The molecular film inhibitor spontaneously spread and form an insoluble molecular film on the gas-liquid interface, changing the state of nitric acid liquid surface and inhibiting the volatilization on the molecular scale. The inhibition rate up to 96% can be achieved below 45 °C within 400 min. Cluster structure simulation and energy barrier calculation is performed to elucidate the inhibition mechanism. Theoretical analysis of energy barrier shows that the specific resistance of the inhibitor significantly increased to 460 s·cm-1 at 45 °C, and the generated energy barrier is about 17,000 kJ·mol-1, which is much higher than the maximum energy required for nitric acid volatilization of 107.97 kJ·mol-1. The molecular film obstruction strategy can effectively inhibit the volatilization of nitric acid. This strategy paves the way for preventing the volatilization of liquid hazardous chemicals in accidental leakage treatment.

Rapid sulfuric acid-dimethylamine nucleation enhanced by nitric acid in polluted regions.

Recent research [Wang et al., Nature 581, 184-189 (2020)] indicates nitric acid (NA) can participate in sulfuric acid (SA)-ammonia (NH3) nucleation in the clean and cold upper free troposphere, whereas NA exhibits no obvious effects at the boundary layer with relatively high temperatures. Herein, considering that an SA-dimethylamine (DMA) nucleation mechanism was detected in megacities [Yao et al., Science 361, 278-281 (2018)], the roles of NA in SA-DMA nucleation are investigated. Different from SA-NH3 nucleation, we found that NA can enhance SA-DMA-based particle formation rates in the polluted atmospheric boundary layer, such as Beijing in winter, with the enhancement up to 80-fold. Moreover, we found that NA can promote the number concentrations of nucleation clusters (up to 27-fold) and contribute 76% of cluster formation pathways at 280 K. The enhancements on particle formation by NA are critical for particulate pollution in the polluted boundary layer with relatively high NA and DMA concentrations.

Nitric oxide recovery from hydrogen combustion streams. A clean pathway for the sustainable production of nitrogen compounds.

This work proves that nitric oxide (NO) can be successfully recovered from hydrogen flue gas streams in nitric acid, opening new pathways for NO control in combustion streams. Recovering NO from hydrogen combustion streams allows for increasing the combustion temperature in the turbine, reducing the fuel consumption per kWh, while obtaining a building block for nitric acid production. The solubility of nitric oxide is determined in amines, ethanol, and nitric acid solutions at a laboratory scale, suitable candidates for nitric oxide absorption. The solubility of nitric oxide in amines and ethanol is very low (0.009 mol/L/bar & 0.018 mol/L/bar respectively) compared with nitric acid (0.23 mol/L/bar), which is in the same range as the solubility of CO2 in amines solutions. Nitric acid, in addition to having good NO solubility, also presents high selectivity towards nitric oxide and easy recovery of nitric oxide by simply raising the temperature. Finally, a fugacity-activity coefficient model combining the Peng-Robinson (PR) equation of state with the Non-Random Two-Liquid (NRTL) activity coefficient model is proposed as a thermodynamic model to represent the NO-HNO3-H2O equilibrium, giving as a result an average absolute deviation between the experimental results and the model predictions of only 5%.

Quantitative and qualitative impacts of nitric acid digestion on microplastic identification via FTIR and Raman spectroscopy, implications for environmental samples.

Quantification and characterization of microplastics, synthetic polymers less than 5 mm in diameter, requires extraction methods that can reduce non-plastic debris without loss or alteration of the polymers. Nitric acid has been used to extract plastic particles from zooplankton and other biota because it completely digests tissue and exoskeletons, thus reducing interferences. While the impact of acid digestion protocols on several polymers has been demonstrated, advice for quantifying microplastic and interpreting their spectra following nitric acid digestion is lacking. Fourier transform infrared (FTIR) and/or Raman spectroscopy was performed on plastics from > 50 common consumer products (including a variety of textiles) pre- and post-nitric acid treatment. The percent match and assigned polymer were tabulated to compare the accuracy of spectral identification before and after nitric acid digestion via two open spectral analysis software. Nylon-66, polyoxymethylene, polyurethane, polyisoprene, nitrile rubber, and polymethyl methacrylate had ≥ 90% mass loss in nitric acid. Other less-impacted polymers changed color, morphology, and/or size following digestion. Thus, using nitric acid digestion for microplastic extraction can impact our understanding of the particle sizes and morphologies ingested in situ. Spectral analysis results were compiled to understand how often (1) the best-hit matches were correct (30-60% of spectra), (2) the best-hit matches exceeding the (arbitrary) threshold of 65% match were correct (53-78% of spectra), and (3) the best-hit matches for anthropogenic polymers were incorrectly identified as natural polymers (12-15% of spectra). Based on these results, advice is provided on how nitric acid digestion can impact microplastics as well as spectral interpretation.

p14ARF ameliorates inflammation and airway remodeling in nitric acid aerosol inhalation-induced bronchiolitis obliterans.

BACKGROUND: To investigate the protective effect of p14ARF in a nitric acid (NA) aerosol inhalation-induced bronchiolitis obliterans (BO) mouse model and its potential regulatory mechanism. METHODS: A BO mouse model was established by NA aerosol inhalation. The expressions of p14ARF, phosphatidylinositol-3-kinase (PI3K), and protein kinase B (AKT) were detected by quantitative reverse transcription PCR (qRT-PCR) and western blot (WB). Hematoxylin (HE) staining, Masson staining, and periodic acid-Schiff (PAS) staining observed pulmonary histological changes. TdT-mediated dUTP nick end labeling (TUNEL) staining detected pulmonary cell apoptosis, and enzyme-linked immunosorbent assay (ELISA) measured matrix metalloproteinase-2 (MMP-2), MMP-9, tissue inhibitor of metalloproteinase-1 (TIMP-1), interleukon-6 (IL-6), and transforminh growth factor-ß (TGF-ß) levels in lung tissue and bronchoalveolar lavage fluid (BALF). RESULTS: The expressions of p14ARF, PI3K, and AKT showed a time gradient change, with a decrease trend (*P < 0.05 and **P < 0.01). Severe inflammatory infiltration and tracheal fibrosis were found in lung tissue in the modeling group (BO group) compared with the control group (Con group). The pH, PaO2, and PaO2/FiO2 values significantly reduced, while the PaCO2 value and the number of TUNEL-positive cells increased in BO group (P < 0.05). In addition, MMP-2, MMP-9, IL-6, and TGF-ß levels remarkably increased, with an increase in the number of white blood cells, neutrophils, and lymphocytes in BO group (P < 0.05). Furthermore, p14ARF up-regulation reversed the trend of the aforementioned indexes in BO mice. CONCLUSIONS: p14ARF ameliorated the inflammatory response and airway remodeling in a BO mouse model via the PI3K/AKT pathway.

Coupling of nitric acid digestion and anion-exchange resin separation for the determination of methylmercury isotopic composition within organisms.

Isotope ratios of methylmercury (MeHg) within organisms can be used to identify sources of MeHg that have accumulated in food webs, but these isotopic compositions are masked in organisms at lower trophic levels by the presence of inorganic mercury (iHg). To facilitate measurement of MeHg isotope ratios in organisms, we developed a method of extracting and isolating MeHg from fish and aquatic invertebrates for compound-specific isotopic analysis involving nitric acid digestion, batch anion-exchange resin separation, and pre-concentration by purge and trap. Recovery of MeHg was quantified after each step in the procedure, and the average cumulative recovery of MeHg was 93.4 ± 2.9% (1 SD, n = 28) for biological reference materials and natural biota samples and 96.9 ± 1.8% (1 SD, n = 5) for aqueous MeHgCl standards. The amount of iHg impurities was also quantified after each step, and the average MeHg purity was 97.8 ± 4.3% (1 SD, n = 28) across all reference materials and natural biota samples after the final separation step. Measured MeHg isotopic compositions of reference materials agreed with literature values obtained using other MeHg separation techniques, and MeHg isotope ratios of aqueous standards, reference materials, and natural biota samples were reproducible. On average, the reproducibility associated with reference material process replicates (2 SD) was 0.10‰ for δ202MeHg and 0.04‰ for Δ199MeHg. This new method provides a streamlined, reliable technique that utilizes a single sample aliquot for MeHg concentration and isotopic analysis. This promotes a tight coupling between MeHg concentration, %MeHg, and Hg isotopic composition, which may be especially beneficial for studying complex food webs with multiple isotopically distinct sources of iHg and/or MeHg.

Preparation of Carbon-Based Solid Acid Catalyst from High-Sulfur Petroleum Coke with Nitric Acid and Ball Milling, and a Computational Evaluation of Inherent Sulfur Conversion Pathways.

A series of petroleum coke (petcoke)-derived solid acid catalysts were prepared via nitric acid treatment with or without ball milling pretreatment. The inherent sulfur in petcoke was converted to sulfonic groups, which were active sites for the esterification of octanoic acid and methanol at 60 °C, with ester yields of 14-43%. More specifically, samples without ball milling treated at 120 °C for 3 h had a total acidity of 4.67 mmol/g, which was 1.6 times that of the samples treated at 80 °C, despite their -SO3H acidities being similar (~0.08 mmol/g). The samples treated for 24 h had higher -SO3H (0.10 mmol/g) and total acidity (5.25 mmol/g) but not increased catalytic activity. Ball milling increased the defects and exposed aromatic hydrogen groups on petcoke, which facilitated further acid oxidation (0.12 mmol -SO3H/g for both materials and total acidity of 5.18 mmol/g and 5.01 mmol/g for BP-N-3/120 and BP-N-8/90, respectively) and an increased ester yield. DFT calculations were used to analyze the pathways of sulfonic acid group formation, and the reaction pathway with NO2• was the most thermodynamically and kinetically favourable. The activities of the prepared catalysts were related to the number of -SO3H acid sites, the total acidity, and the oxygen content, with the latter two factors having a negative impact.

Efficient and Selective Adsorption of Cationic Dye Malachite Green by Kiwi-Peel-Based Biosorbents.

In this study, pristine kiwi peel (KP) and nitric acid modified kiwi peel (NA-KP) based adsorbents were prepared and evaluated for selective removal of cationic dye. The morphology and chemical structure of KP and NA-KP were fully characterized and compared, and results showed nitric acid modification introduced more functional groups. Moreover, the adsorption kinetics and isotherms of malachite green (MG) by KP and NA-KP were investigated and discussed. The results showed that the adsorption process of MG onto KP followed a pseudo-second-order kinetic model and the Langmuir isotherm model, while the adsorption process of MG onto NA-KP followed a pseudo-first-order kinetic model and the Freundlich isotherm model. Notably, the Langmuir maximum adsorption capacity of NA-KP was 580.61 mg g-1, which was superior to that of KP (297.15 mg g-1). Furthermore, thermodynamic studies demonstrated the feasible, spontaneous, and endothermic nature of the adsorption process of MG by NA-KP. Importantly, NA-KP showed superior selectivity to KP towards cationic dye MG against anionic dye methyl orange (MO). When the molar ratio of MG/MO was 1:1, the separation factor (αMG/MO) of NA-KP was 698.10, which was 5.93 times of KP. In addition, hydrogen bonding, π-π interactions, and electrostatic interaction played important roles during the MG adsorption process by NA-KP. This work provided a low-cost, eco-friendly, and efficient option for the selective removal of cationic dye from dyeing wastewater.

Nitric Acid-Treated Blue Coke-Based Activated Carbon's Structural Characteristics and Its Application in Hexavalent Chromium-Containing Wastewater Treatment.

This study primarily focused on the efficient transformation of low-priced blue coke powder into a high-capacity adsorbent and aimed to address the pollution issue of hexavalent chromium (Cr (VI))-laden wastewater and to facilitate the effective utilization of blue coke powder. A two-step method was utilized to fabricate a blue coke-based nitric acid-modified material (LCN), and the impact of nitric acid modification on the material's structure and its efficacy in treating Cr (VI)-contaminated wastewater was evaluated. Our experimental results illustrated that, under identical conditions, LCN exhibited superior performance for Cr (VI) treatment compared to the method employing only potassium hydroxide (LCK). The specific surface area and pore volume of LCN were 1.39 and 1.36 times greater than those of LCK, respectively. Further chemical composition analysis revealed that the functional group structure on the LCN surface was more conducive to Cr (VI) adsorption. The highest amount of Cr (VI) that LCN could bind was measured at 181.962 mg/g at 318 K. This was mostly due to chemisorption, which is dominated by redox reactions. The Cr (VI) removal process by LCN was identified to be a spontaneous, exothermic, and entropy-increasing process. Several tests on recycling and reuse showed that LCN is a stable and effective chromium-containing wastewater adsorbent, showing that it could be used in many situations.

Significant parameter for controlling the partition of ambient nitrate species between HNO3(g) and NH4NO3(p).

The equilibrium between nitric acid gas (HNO3(g)) and ammonium nitrate aerosol (NH4NO3(p)) in ambient air was studied based on the monitoring data obtained using a five-stage filter-pack system, in which the fine aerosol and the coarse aerosol were separately collected; this made it possible to evaluate the actual situation of the equilibrium more accurately. The partition between HNO3(g) and coarse particulate nitrate (c-NO3-(p)), as well as that between HNO3(g) and fine particulate nitrate (f-NO3-(p)), could be evaluated individually thanks to the classification separation of the aerosol by size. The c-particle proportion c-NO3-(p)/(c-NO3-(p) + HNO3(g)) between HNO3(g) and c-NO3-(p) had a weak negative correlation (r = -0.46, p<0.001) with air temperature; in contrast, the f-particle proportion f-NO3-(p)/(f-NO3-(p) + HNO3(g)) between HNO3(g) and f-NO3-(p) had a moderate negative correlation (r = -0.80, p<0.001) with air temperature in total; furthermore, the f-particle proportion had an interesting and discriminative dependence on air temperature which could be divided into two regions by an air temperature around 15°C. The condition of high air temperature accompanied by high relative humidity frequently resulted in the deliquescent state of NH4NO3(p), providing the disconnect from the theoretical prediction for the products of [NH3(g)] and [HNO3(g)] ([NH3(g)][HNO3(g)]) by Seinfeld and Pandis (1998).

State of gaseous air pollutants and resulting health effects in Karachi, Pakistan.

Karachi, Pakistan, is a priority site for air pollution research due to high emissions of air pollutants from vehicular traffic, industrial activities, and biomass burning, as well as rapid growth in population. The objectives of this study were to investigate the levels of gaseous pollutants (NO, NO2, O3, HNO3, and SO2) in Karachi, to determine temporal and seasonal variations, to compare Karachi's air quality with other urban centers, to identify relationships with meteorological conditions, to identify source characterization, and to perform a backward-in-time trajectory analysis and a health impact assessment. Daily samples of gaseous pollutants were collected for six consecutive weeks in each of the four seasons for a year. Daily maximum concentrations of NO (90 parts per billion by volume (ppbv)), NO2 (28.1 ppbv), O3 (57.8 ppbv), and SO2 (331 ppbv) were recorded in fall, while HNO3 (9129 parts per trillion by volume (pptv)) was recorded in spring. Seasonal average concentrations were high in winter for NO (9.47 ± 7.82 ppbv), NO2 (4.84 ± 3.35 ppbv), and O3 (8.92 ± 7.65 ppbv), while HNO3 (629 ± 1316 pptv) and SO2 (20.2 ± 39.4 ppbv) were high in spring and fall, respectively. The observed SO2 seasonal average concentration in fall (20.2 ± 39.4) was 5 times higher than that in summer (3.97 ± 2.77) with the fall 24-h average (120 ppbv) exceeding the WHO daily guideline (7.64 ppbv) by a factor of about 15.7. A health impact assessment estimated an increase of 1200 and 569 deaths due to short-term exposure to SO2 in fall and spring, respectively. Chronic daily intake estimated risk per 1000 was 0.99, 0.47, 0.45, and 0.26 for SO2 in fall, NO in winter, O3 in winter, and NO2 in spring, respectively. This study confirms the effect of poor urban air quality on public health and demonstrated the influence of photochemical reactions as well as unfavorable meteorological conditions on the formation of secondary pollutants.

Acid deposition at higher acidity weakens the antagonistic responses during the co-decomposition of two Asteraceae invasive plants.

Co-invasion by two invasive plant species (IPS) can occur in the same habitat. Diversified acid deposition may change the co-invasion process by altering litter decomposition and plant-soil feedback signalling. This study examined the co-decomposition of two Asteraceae IPS (Solidago canadensis L. and Bidens pilosa L.) on litter decomposition rate, soil enzyme activities, and soil N-fixing bacterial communities under diversified acid deposition (mixed acid deposition at pH 5.6 and at pH 4.5, sulfuric acid at pH 4.5, and nitric acid at pH 4.5). B. pilosa litter degraded faster than S. canadensis litter. Acid deposition at higher acidity accelerated the decomposition rate of both pure S. canadensis litter and the equally mixed litters from the two Asteraceae IPS. Antagonistic responses may occur during the co-decomposition of the two Asteraceae IPS with mixed acid deposition, regardless of the pH, as well as with nitric acid deposition at pH 4.5; in contrast, there may be neutral responses for the co-decomposition process with sulfuric acid at pH 4.5. The type of acid deposited may be one of the key factors affecting the intensity of the mixing effect affecting the co-decomposition. Acid deposition at higher acidity weakened the antagonistic responses for the co-decomposition of the two Asteraceae IPS compared with the response to weak acids. Together, these results indicate that acid deposition at higher acidity could facilitate the co-invasion of the two Asteraceae IPS mainly through accelerated litter decomposition as well as weakened antagonistic responses for co-decomposition.

A High-Precision Mid-Infrared Spectrometer for Ambient HNO3 Measurements.

Precise and accurate measurements of ambient HNO3 are crucial for understanding various atmospheric processes, but its ultra-low trace amounts and the high polarity of HNO3 have strongly hindered routine, widespread, direct measurements of HNO3 and restricted field studies to mostly short-term, localized measurement campaigns. Here, we present a custom field-deployable direct absorption laser spectrometer and demonstrate its analytical capabilities for in situ atmospheric HNO3 measurements. Detailed laboratory characterizations with a particular focus on the instrument response under representative conditions for tropospheric measurements, i.e., the humidity, spectral interference, changing HNO3 amount fractions, and air-sampling-related artifacts, revealed the key aspects of our method: (i) a good linear response (R2 > 0.98) between 0 and 25 nmol·mol−1 in both dry and humid conditions with a limit of detection of 95 pmol·mol−1; (ii) a discrepancy of 20% between the spectroscopically derived amount fractions and indirect measurements using liquid trapping and ion chromatography; (iii) a systematic spectral bias due to water vapor. The spectrometer was deployed in a three-week field measurement campaign to continuously monitor the HNO3 amount fraction in ambient air. The measured values varied between 0.1 ppb and 0.8 ppb and correlated well with the daily total nitrates measured using a filter trapping method.

Electrochemical Synthesis of Nitric Acid from Nitrogen Oxidation.

Nitric acid is widely applied in agriculture and industry. The present manufacturing process via a combination of the Haber-Bosch process and the Ostwald oxidation process is accompanied by massive energy consumption and greenhouse gas emissions. The direct electrocatalytic nitrogen oxidation reaction (NOR) to nitric acid is a promising alternative, especially when it is driven by renewable energy sources. The standardization of performance evaluation is the prerequisite for the design and synthesis of efficient electrocatalysts for NOR. In this context, this Minireview first discusses the history of the development of HNO3 manufacturing and the possible reaction mechanisms for electrocatalytic NOR. Then, a strict protocol for electrochemical NOR experiments is recommended. Finally, general research targets associated with techno-economic analysis, challenges, and prospects for NOR are summarized for future studies.

Simple and Fast High-Yield Synthesis of Silver Nanowires.

Silver nanowires (AgNWs) combine high electrical conductivity with low light extinction in the visible and are used in a wide range of applications, from transparent electrodes, to temperature and pressure sensors. The most common strategy for the production of AgNWs is the polyol synthesis, which always leads to the formation of silver nanoparticles as byproducts. These nanoparticles degrade the performance of AgNWs' based devices and have to be eliminated by several purification steps. Here, we report a simple and fast synthesis of AgNWs with minimal formation of byproducts, as confirmed by the spectral purity of the final solution. Our synthetic strategy relies on the use of freshly prepared AgCl and on the minimization of gas evolution inside the reaction vessel. The observed synthetic improvements can be of general validity for the polyol synthesis of metallic nanostructures of different shapes and compositions.

Carbon Nanostructures Derived through Hypergolic Reaction of Conductive Polymers with Fuming Nitric Acid at Ambient Conditions.

Hypergolic systems rely on organic fuel and a powerful oxidizer that spontaneously ignites upon contact without any external ignition source. Although their main utilization pertains to rocket fuels and propellants, it is only recently that hypergolics has been established from our group as a new general method for the synthesis of different morphologies of carbon nanostructures depending on the hypergolic pair (organic fuel-oxidizer). In search of new pairs, the hypergolic mixture described here contains polyaniline as the organic source of carbon and fuming nitric acid as strong oxidizer. Specifically, the two reagents react rapidly and spontaneously upon contact at ambient conditions to afford carbon nanosheets. Further liquid-phase exfoliation of the nanosheets in dimethylformamide results in dispersed single layers exhibiting strong Tyndall effect. The method can be extended to other conductive polymers, such as polythiophene and polypyrrole, leading to the formation of different type carbon nanostructures (e.g., photolumincent carbon dots). Apart from being a new synthesis pathway towards carbon nanomaterials and a new type of reaction for conductive polymers, the present hypergolic pairs also provide a novel set of rocket bipropellants based on conductive polymers.

Design of Extractants for F-Block Elements in a Series of (2-(Diphenylphosphoryl)methoxyphenyl)diphenylphosphine Oxide Derivatives: Synthesis, Quantum-Chemical, and Extraction Studies.

With the aim to find new efficient extractants for recovery of f-block elements from processing wastes of different origin, we have compared a series of phosphoryl-containing podands, including (2-(diphenylphosphorylmethoxy)phenyl)diphenylphosphine oxide 1 and its analogues 5-7, where the ArP(O)Ph2 group of phosphine oxide type is replaced by phosphonic fragments. Quantum-chemical modelling of the structures of phosphoryl-containing podands 1 and 5-7 has been performed, which was later confirmed by the data of X-ray diffraction. The features of extraction of nitric acid, as well as U(VI), Th(IV), Nd(III), and Ho(III) with compounds 1 and 5-7 from nitric acid media into 1,2-dichloroethane have been studied. The compositions of extracted complexes have been determined.

Synergistic effect of UV, thermal, and chemical treatment on biological degradation of low-density polyethylene (LDPE) by Thermomyces lanuginosus.

The present analysis deals with the ability of Thermomyces lanuginosus to degrade pre-treated low-density polyethylene (LDPE). The synergistic effect of UV irradiation, heat, and acid pre-treatments on the biodegradability of the polymer was thoroughly assessed. Oxidative structural modifications such as the appearance of carboxylate and carbonyl groups in LDPE chains were recorded post the UV and heat treatments. Furthermore, the nitric acid treatment incorporated NO2 groups into the polymer matrix. Alterations in the polymer thermal stabilities and surface morphologies after each pre-treatment were analyzed using thermogravimetric analysis and scanning electron microscopy (SEM), respectively. The gravimetric analysis revealed a reduction in the weight of the pre-treated LDPE films by 9.21 ± 0.84% after 1 month of the incubation period with Thermomyces lanuginosus. An increase in the thermal stability, disappearance of the incorporated hydrophilic functional groups, and reduction in the carbon content of the polymer samples post the incubation period further justified the biodegradation process. SEM analysis showed modifications in the morphology and texture patterns in pre-treated LDPE after inoculation with Thermomyces lanuginosus. The findings suggest that Thermomyces lanuginosus could be efficient for the decomposition of pre-treated LDPE under laboratory conditions.

Chemistry of NOx and HNO3 Molecules with Gas-Phase Hydrated O.- and OH- Ions.

The gas-phase reactions of O. - (H2 O)n and OH- (H2 O)n , n=20-38, with nitrogen-containing atmospherically relevant molecules, namely NOx and HNO3 , are studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and theoretically with the use of DFT calculations. Hydrated O. - anions oxidize NO. and NO2 . to NO2 - and NO3 - through a strongly exothermic reaction with enthalpy of -263±47 kJ mol-1 and -286±42 kJ mol-1 , indicating a covalent bond formation. Comparison of the rate coefficients with collision models shows that the reactions are kinetically slow with 3.3 and 6.5 % collision efficiency. Reactions between hydrated OH- anions and nitric oxides were not observed in the present experiment and are most likely thermodynamically hindered. In contrast, both hydrated anions are reactive toward HNO3 through proton transfer from nitric acid, yielding hydrated NO3 - . Although HNO3 is efficiently picked-up by the water clusters, forming (HNO3 )0-2 (H2 O)m NO3 - clusters, the overall kinetics of nitrate formation are slow and correspond to an efficiency below 10 %. Combination of the measured reaction thermochemistry with literature values in thermochemical cycles yields ΔHf (O- (aq.))=48±42 kJ mol-1 and ΔHf (NO2 - (aq.))=-125±63 kJ mol-1 .