N-doping offering higher photodegradation performance of dissolved black carbon for organic pollutants: experimental and theoretical studies

We investigated the influence mechanism of N-doping for dissolved black carbon(DBC)photodegradation of organic pollutants.The degradation performance of N-doped dissolved black carbon(NDBC)for tetracycline(TC)(71%)is better than that for methylene blue(MB)(28%)under irradiation.These levels are both better than DBC degradation performances for TC(68%)and MB(18%)under irradiation.Reactive species quenching experiments suggest that h and-O,are the main reactive species for NDBC photodegraded TC,while-OH and h*are the main reactive species for NDBC photodegraded MB.-OH is not observed during DBC photodegradation of MB.This is likely because N-doping increases valence-band(VB)energy from 1.55 eV in DBC to 2.04 eV in NDBC;the latter is strong enough to oxidize water to form-OH.Additionally,N-doping increases the DBC band gap of 2.29 to 2.62 eV in NDBC,resulting in a higher separation efficiency of photo-generated electrons-holes in NDBC than in DBC.AIl these factors give NDBC stronger photodegradation performance for TC and MB than DBC.High-performance liquid chromatography-mass spectrometry(HPLC-MS)characterization and toxicity evaluation with the quantitative structure-activity relationship(QSAR)method suggest that TC photodegradation intermediates produced by NDBC have less aromatic structure and are less toxic than those produced by DBC.We adopted a theoretical approach to clarify the relationship between the surface groups of NDBC and the photoactive species produced.Our results add to the understanding of the photochemical behavior of NDBC.

Characteristics of typical dissolved black carbons and their influence on the formation of disinfection by-products in chlor(am)ination

Dissolved black carbon(DBC)released from biochar can be one of the potential disinfection by-products(DBPs)precursors in the dissolved organic matter pool.However,the physiochemical and structural properties of DBC and the effects on the development of DBPs and DBP formation potential(DBPFP)during the disinfection process remain unclear.In this study,the characteristics of two kinds of DBC,namely,animal-derived DBC(poultry litter DBC,PL-DBC)and plant-derived DBC(wheat straw DBC,WS-DBC),were investigated.The effects of different kinds of DBC on the evolution of DBPs and DBPFP in chlorine and chloramine disinfection processes were compared with natural organic matter(NOM).The results showed that the total DBPs concentrations derived from PL-DBC,WS-DBC and NOM were similar during chlorination(i.e.,61.23µg/L,64.59µg/L and 64.66µg/L,respectively)and chloramination(i.e.,44.63µg/L,44.42µg/L and 45.58µg/L,respectively).The lower total DBPs and DBPFP concentrations in chloramination could be attributed to the fact that the introduction of ammonia in chloramine inhibited the breaking of the bond between the disinfectant and the active group of the precursor.Additionally,DBC presented much lower total DBPFP concentrations than NOM in both chlorination and chloramination.However,both kinds of DBC tended to form more monochloroacetic acids and haloacetamides than NOM,which could result from the higher organic strength,higher protein matter,and nitrogen-rich soluble microbial products of DBC.