Catalytic Degradation of 4-Ethylpyridine in Water by Heterogeneous Photo-Fenton Process

In this work, the degradation of 4-ethylpyridine (4EP) in water by a heterogeneous photo-Fenton process (H2O2/Fe3O4/ultraviolet irradiation (UV)) was investigated. More rapid and effective 4EP degradation was obtained with H2O2/Fe3O4/UV than Fenton-like (H2O2/Fe3O4) and UV/H2O2, which is due to the larger production of hydroxyl radicals from the chemical and photolytic decomposition of H2O2. The operational conditions were varied during 4EP degradation experiments to evaluate the effects of pH, catalyst, concentration, and temperature on the kinetics and efficiency of H2O2/Fe3O4/UV oxidation. Under optimal conditions (100 mg/L 4EP, [H2O2] = 1000 mg/L, Fe3O4 = 40 mg/L, pH = 3 and room temperature, 300 rpm), 4EP was totally declined and more than 93% of the total organic carbon (TOC) was eliminated. Liquid chromatography analysis confirmed the formation of aromatic and aliphatic intermediates (4-hydroxypyridine, 4-pyridone, malonic, oxalic, and formic acids) that resulted in being mineralized. Ion chromatography analysis demonstrated the stoichiometric release of NH4+ ions during 4EP degradation by heterogeneous photo-Fenton oxidation. The reuse of the heterogeneous catalyst was evaluated after chemical and heat treatment at different temperatures. The heat-treated catalyst at 500 °C presented similar activity than the pristine Fe3O4. Accordingly, heterogeneous photo-Fenton oxidation can be an alternative method to treat wastewaters and groundwater contaminated with pyridine derivatives and other organic micropollutants. The combination of heterogeneous photo-Fenton oxidation with classical biological methods can be proposed to reduce the overall cost of the treatment in large-scale water treatment plants.

Identification and Migration Studies of Photolytic Decomposition Products of UV-Photoinitiators in Food Packaging

UV-curable inks, coatings, and adhesives are being increasingly used in food packaging systems. When exposed to UV energy, UV-photoinitiators (PI’s) present in the formulations produce free radicals which catalyze polymerization of monomers and pre-polymers into resins. In addition to photopolymerization, other free radical reactions occur in these systems resulting in the formation of chemically varied photolytic decomposition products, many of which are low molecular weight chemical species with high migration potential. This research conducted model experiments in which 24 commonly used PI’s were exposed to UV-energy at the typical upper limit of commercial UV-printing press conditions. UV-irradiated PI’s were analyzed by gas chromatography-mass spectrometry (GC-MS) and electrospray-mass spectrometry (ESI-MS) in order to identify photolytic decomposition products. Subsequently, migration studies of 258 UV-cure food packaging samples were conducted using GC-MS; PI’s and photolytic decomposition products were found in nearly all samples analyzed. One hundred-thirteen photolytic decomposition products were identified. Eighteen intact PI’s and 21 photolytic decomposition products were observed as migrants from the 258 samples analyzed, and these were evaluated for frequency of occurrence and migratory concentration range. The most commonly observed PI’s were 2-hydroxy-2-methylpropiophenone and benzophenone. The most commonly observed photolytic decomposition products were 2,4,6-trimethylbenzaldehyde and 1-phenyl-2-butanone. This compilation of PI photolytic decomposition data and associated migration data will aid industry in identifying and tracing non-intentionally added substances (NIAS) in food packaging materials.

Photocatalytic Degradation of Some Polyolefin-TiO2 Composites Evaluated by Molecular Spectroscopy

The photochemical degradation of polyolefin-TiO2 composite films was investigated and described in relationship with the concentration of photocatalyst and after different exposure times. UV-Vis-NIR and IR spectra reveal the presence of various degradation products, which are in direct connection with the photodecomposition mechanism. Various ratios between the absorbance of some typical IR characteristic bands can lead to the evaluation of photocomposition of polyethylene and polypropylene composite films containing TiO2 nanoparticles.The results show that the photocatalytic degradation of composites is significantly faster than the simple photolytic decomposition of pure polypropylene and polyethylene and could be used as a solution for the destruction of this type of wastes.

A comparison of HONO budgets for two measurement heights at a field station within the boreal forest in Finland

Atmospheric concentrations of nitrous acid (HONO), one of the major precursors of the hydroxyl radical (OH) in the troposphere, significantly exceed the values predicted by the assumption of a photostationary state (PSS) during daytime. Therefore, additional sources of HONO were intensively investigated in the last decades. This study presents budget calculations of HONO based on simultaneous measurements of all relevant species, including HONO and OH at two different measurement heights, i.e. 1 m above the ground and about 2 to 3 m above the canopy (24 m above the ground), conducted in a boreal forest environment. We observed mean HONO concentrations of about 6.5 × 108 molecules cm−3 (26 ppt) during daytime, more than 20 times higher than expected from the PSS of 0.2 × 108 molecules cm−3 (1 ppt). To close the budgets at both heights, a strong additional source term during daytime is required. This unidentified source is at its maximum at noon (up to 1.1 × 106 molecules cm−3 s−1, 160 ppt h−1) and in general up to 2.3 times stronger above the canopy than close to the ground. The insignificance of known gas phase reactions and other processes like dry deposition or advection compared to the photolytic decomposition of HONO at this measurement site was an ideal prerequisite to study possible correlations of this unknown term to proposed HONO sources. But neither the proposed emissions from soils nor the proposed photolysis of adsorbed HNO3 contributed substantially to the unknown source. However, the unknown source was found to be perfectly correlated to the unbalanced photolytic loss of HONO.

Comparison of HONO budgets for two measurement heights at a field station within the boreal forest (SMEAR II – HUMPPA-COPEC 2010)

Atmospheric concentrations of nitrous acid (HONO), one of the major precursors of the hydroxyl radical (OH) in the troposphere, normally exceed by far the values predicted by the assumption of a photostationary state (PSS) during daytime. Therefore, additional sources of HONO were intensively investigated in the last decades. Here, we present budget calculations of HONO based on simultaneous measurements of all relevant species including HONO and OH at two different measurement heights, i.e. 1 m above ground and about 2 to 3 m above canopy (24 m above ground), conducted in boreal forest environment. We observed mean HONO concentrations during daytime of about 6.5 × 108 molecules cm−3 (26 ppt), more than twenty times higher than expected from the PSS, 0.2 × 108 molecules cm−3 (1 ppt). To close the budgets in both heights a strong additional source term during daytime is required. This unidentified source is maximal at noon (up to 1.1 × 106 molecules cm−3 s−1, 160 ppt h−1) and in general up to 2.3 times stronger above the canopy than close to the ground. The insignificance of known gas phase reactions and also other processes like dry deposition or advection compared to the photolytic decomposition of HONO at this measurement site was an ideal prerequisite to study possible correlations of this unknown term to proposed HONO sources. But neither the proposed emissions from soils nor the proposed photolysis of adsorbed HNO3 contributed substantially to the unknown source. However, the unknown source was found to be perfectly correlated to the unbalanced photolytic loss of HONO.