Photochemical (UV-vis/H2O2) degradation of carotenoids: Kinetics and molecular end products.

Constraining the formation mechanisms of organic matter that persists in aquatic reservoirs is important for determining the reactivity and fate of carbon and nutrients in these environments. Recent studies have linked dissolved organic matter (DOM) accumulating in the ocean to linear terpenoid structures, and carotenoid degradation products have been proposed as potential precursors. The prevalence of reactive oxygen species in aquatic environments and their potential to be quenched by carotenoids led us to examine radical-assisted photochemical degradation of carotenoids as a potential mechanism for DOM formation and transformation. Experiments were conducted with aggregates of ß-carotene, astaxanthin, fucoxanthin and meso-zeaxanthin in THF:H2O under solar light irradiation assisted by hydrogen peroxide (UV-Vis/H2O2). Based on the fine structure of UV-Vis spectra, it was determined that ß-carotene and meso-zeaxanthin formed J-type aggregates in experimental solutions, while astaxanthin and fucoxanthin formed H2-type aggregates, consistent with their structural characteristics. All carotenoids degraded under the combined influence of photolysis and OH scavenging, with fucoxanthin exhibiting the fastest degradation kinetics (kPO = 3.69 10-3 s-1) and meso-zeaxanthin the slowest (kPO = 4.37 10-4 s-1). The major degradation products detected by electrospray ionization (ESI) tandem mass spectrometry (MS/MS) were apo-aldehydes and apo-ketones, with the latter tending to accumulate, but epoxidation of the carotenoids also took place, and longer irradiation times resulted in lower molecular weight products. Reaction kinetics and accumulating carotenoid oxidation products identified in this study provide potential formation mechanisms and biomarkers for examining DOM cycling.

The role of natural organic matter in nitrite formation by LP-UV/H2O2 treatment of nitrate-rich water.

The role of natural organic matter (NOM) on nitrite formation from nitrate photolysis by low pressure ultraviolet lamp (LP-UV) photolysis and LP-UV/H2O2 treatment was investigated. Nitrate levels up to the WHO guideline maximum of 50 mg NO3-/L were used in tests. The presence of 4 mg/L Suwannee River natural organic matter (NOM) led to increased nitrite yields compared to NOM-free controls. This was caused partly by NOM scavenging of OH radicals, preserving the produced NO2- as well as the ONOO- that leads to NO2- formation, but also via the production of radical species (1O2, O2- and OH) by the photolysis of NOM. In addition, solvated electrons formed by NOM photolysis may reduce nitrate directly to nitrite. For comparison, Nordic Lake NOM, representative of aquatic NOM, as well as Pony Lake NOM, which had a greater nitrogen content (6.51% w/w) than the other two types of NOM, were investigated, yielding similar nitrite levels as Suwannee River NOM. The results suggest that neither the type nor the nitrogen content of the NOM have an effect on the nitrite yields obtained over the range of UV/H2O2 doses applied (UV fluences of 500-2100 mJ/cm2 and hydrogen peroxide doses of 10, 25, and 50 mg/L). The findings indicate that for UV fluences above 1500 mJ/cm2 the resulting nitrite concentration can exceed the 0.1 mg/L EU regulatory limit for nitrite, suggesting that nitrite formation by LP-UV advanced oxidation of nitrate-rich waters is important to consider.

Low pressure UV/H2O2 treatment for the degradation of the pesticides metaldehyde, clopyralid and mecoprop - Kinetics and reaction product formation.

The degradation kinetics of three pesticides - metaldehyde, clopyralid and mecoprop - by ultraviolet photolysis and hydroxyl radical oxidation by low pressure ultraviolet hydrogen peroxide (LP-UV/H2O2) advanced oxidation was determined. Mecoprop was susceptible to both LP-UV photolysis and hydroxyl radical oxidation, and exhibited the fastest degradation kinetics, achieving 99.6% (2.4-log) degradation with a UV fluence of 800 mJ/cm(2) and 5 mg/L hydrogen peroxide. Metaldehyde was poorly degraded by LP-UV photolysis while 97.7% (1.6-log) degradation was achieved with LP-UV/H2O2 treatment at the maximum tested UV fluence of 1000 mJ/cm(2) and 15 mg/L hydrogen peroxide. Clopyralid was hardly susceptible to LP-UV photolysis and exhibited the lowest degradation by LP-UV/H2O2 among the three pesticides. The second-order reaction rate constants for the reactions between the pesticides and OH-radicals were calculated applying a kinetic model for LP-UV/H2O2 treatment to be 3.6 × 10(8), 2.0 × 10(8) and 1.1 × 10(9) M(-1) s(-1) for metaldehyde, clopyralid and mecoprop, respectively. The main LP-UV photolysis reaction product from mecoprop was 2-(4-hydroxy-2-methylphenoxy) propanoic acid, while photo-oxidation by LP-UV/H2O2 treatment formed several oxidation products. The photo-oxidation of clopyralid involved either hydroxylation or dechlorination of the ring, while metaldehyde underwent hydroxylation and produced acetic acid as a major end product. Based on the findings, degradation pathways for the three pesticides by LP-UV/H2O2 treatment were proposed.