BCH1 expression pattern contributes to the fruit carotenoid diversity between peach and apricot.

Peach (Prunus persica L. Batsch) and apricot (Prunus armeniaca L.) are two species of economic importance for fruit production in the genus Prunus. Peach and apricot fruits exhibit significant differences in carotenoid levels and profiles. HPLC-PAD analysis showed that a greater content of ß-carotene in mature apricot fruits is primarily responsible for orange color, while peach fruits showed a prominent accumulation of xanthophylls (violaxanthin and cryptoxanthin) with yellow color. There are two ß-carotene hydroxylase genes in both peach and apricot genomes. Transcriptional analysis revealed that BCH1 expresses highly in peach but lowly in apricot fruit, showing a correlation with peach and apricot fruit carotenoid profiles. By using a carotenoid engineered bacterial system, it was demonstrated that there was no difference in the BCH1 enzymatic activity between peach and apricot. Comparative analysis about the putative cis-acting regulatory elements between peach and apricot BCH1 promoters provided important information for our understanding of the differences in promoter activity of the BCH1 genes in peach and apricot. Therefore, we investigated the promoter activity of BCH1 gene through a GUS detection system, and confirmed that the difference in the transcription level of the BCH1 gene resulted from the difference of the promoter function. This study provides important perspective to understanding the diversity of carotenoid accumulation in Prunus fruits such as peach and apricot. In particular, BCH1 gene is proposed as a main predictor for ß-carotene content in peach and apricot fruits during the ripening process.

Accelerated oxidation of the emerging brominated flame retardant tetrabromobisphenol S by unactivated peroxymonosulfate: The role of bromine catalysis and formation of disinfection byproducts.

Tetrabromobisphenol S (TBBPS) is an emerging brominated flame retardant (BFR) that can cause endocrinological abnormalities in aquatic species and is neurotoxic and cytotoxic to humans. Herein, we investigated the oxidation of TBBPS by unactivated peroxymonosulfate (PMS) in aqueous solution. Results show that PMS was capable of oxidizing TBBPS without activation, and the transformation of TBBPS was pH-dependent. Interestingly, the unactivated PMS oxidation of TBBPS exhibited an autocatalytic behavior. Radical quenching experiments and electron paramagnetic resonance (EPR) analyzes ruled out the involvement of hydroxyl radical (HO•) and sulfate radical (SO4•­) as reactive species. While the generation of singlet oxygen (1O2) was confirmed in PMS solution, it was also not responsible for TBBPS oxidation. The bromine substituents are believed to be responsible for the autocatalysis observed during PMS oxidation. We propose that the initial oxidation of TBBPS by PMS resulted in the release of bromide ions (Br-) via debromination, which could be rapidly oxidized to hypobromous acid (HOBr). 3,5-Dimethyl-1H-pyrazole (DMPZ) trapping coupled with liquid chromatography-mass spectrometry (LC-MS) analysis evidenced the formation of HOBr in PMS/TBBPS system. Therefore, the presence of Br-, albeit at trace level, could significantly accelerate the oxidation of TBBPS in PMS solution via HOBr formation. The intermediate products of TBBPS were identified by solid phase extraction (SPE) coupled with high resolution-mass spectrometry (HR-MS). The oxidation of TBBPS by unactivated PMS was likely initiated through a single electron transfer mechanism, and the transformation pathways included ß-scission, debromination, and cross-coupling reactions. Further oxidation and ring-opening of the intermediates yielded three brominated disinfection byproducts (Br-DBPs), including bromoform (CHBr3), mono-, and di-bromoacetic acids (MBAA and DBAA), as quantified by gas chromatography (GC). The presence of natural organic matter (NOM) inhibited the oxidation of TBBPS and reduced the yields of Br-DBPs. Our results indicate that unactivated PMS was efficient in the abatement of TBBPS in aqueous solution due to the accelerated oxidation by bromine catalysis; however, the formation of brominated intermediate products and Br-DBPs should be scrutinized due to their potential carcinogenicity and mutagenicity.

Formation of chloronitrophenols upon sulfate radical-based oxidation of 2-chlorophenol in the presence of nitrite.

Sulfate radical (SO4-)-based advanced oxidation processes (SR-AOPs) are promising in-situ chemical oxidation technologies widely applied for soil/groundwater remediation. The presence of non-target water constituents may interfere the abatement of contaminants by SR-AOPs as well as result in the formation of unintended byproducts. Herein, we reported the formation of toxic chloronitrophenols during thermally activated persulfate oxidation of 2-chlorophenol (2CP) in the presence of nitrite (NO2-). 2-Chloro-4-nitrophenol (2C4NP) and 2-chloro-6-nitrophenol (2C6NP) were identified as nitrated byproducts of 2CP with total yield up to 90%. The formation of nitrated byproducts is a result of coupling reaction between 2CP phenoxyl radical (ClPhO) and nitrogen dioxide radical (NO2). As a critical step, the formation of ClPhO was supported by density functional theory (DFT) computation. Both 2C4NP and 2C6NP could convert to 2-chloro-4,6-dinitrophenol (2C46DNP) upon further treatment via a denitration-renitration process. The formation rate of 2C4NP and 2C6NP was closely dependent on the concentration of NO2-, solution pH, and natural water constituents. ECOSAR calculation suggests that chloronitrophenols are generally more hydrophobic and ecotoxic than 2CP. Our result therefore reveals the potential risks in the abatement of chlorophenols by SR-AOP, particularly when high level of NO2- is present in water matrix.