Synthesis of typical sulfonamide antibiotics with [14C]- and [13C]-labeling on the phenyl ring for use in environmental studies.

Background: Due to their widespread use, sulfonamide antibiotics (SAs) have become ubiquitous environmental contaminants and thus a cause of public concern. However, a complete understanding of the behavior of these pollutants in complex environmental systems has been hampered by the unavailability and high cost of isotopically labeled SAs. Results: Using commercially available uniformly [14C]- and [13C]-labeled aniline as starting materials, we synthesized [phenyl-ring-14C]- and [phenyl-ring-13C]-labeled sulfamethoxazole (SMX), sulfamonomethoxine (SMM), and sulfadiazine (SDZ) in four-step (via the condensation of labeled N-acetylsulfanilyl chloride and aminoheterocycles) or five-step (via the condensation of labeled N-acetylsulfonamide and chloroheterocycles) reactions, with good yields (5.0-22.5% and 28.1-54.1% for [14C]- and [13C]-labeled SAs, respectively) and high purities (> 98.0%). Conclusion: The synthesis of [14C]-labeled SAs in milligram amounts enables the preparation of labeled SAs with high specific radioactivity. The efficient and feasible methods described herein can be applied to the production of a variety of [14C]- or [13C]-labeled SAs for studies on their environmental behavior, including the fate, transformation, and bioaccumulation of these antibiotics in soils and aqueous systems. Supplementary Information: The online version contains supplementary material available at 10.1186/s12302-022-00598-z.

Fate of lower-brominated diphenyl ethers (LBDEs) in a red soil - Application of 14C-labelling.

Lower-brominated diphenyl ethers (LBDEs) occur ubiquitously in soil, however their fate there has not been well evaluated, mainly owing to that the unavailability of commercial radioactively labelled LBDE congeners hampers the investigation on fate of LBDEs in the environment with complex matrixes, such as soil and sediment. Here, we successfully synthesized three congeners of LBDEs, i.e., 4-bromodiphenyl ether (BDE3), 4,4'-dibromodiphenyl ether (BDE15), and 2,2',4,4'-tetrabromodiphenyl ether (BDE47), with 14C-labelling on one aromatic ring, starting from commercially available 14C-labelled phenol in two steps with high yields and high radiochemical purities. Using the 14C-labelled congeners, we studied the fate of LBDEs in a red soil under oxic conditions, where LBDEs have been frequently detected in high levels. The major fate of the LBDE congeners in the soil was formation of NERs, followed by mineralization to CO2, while no transformation product was detected in the soil after incubation for 105 days. The mineralization strongly decreased with increasing number of the bromine atom on the congener molecule, amounting to 10.4 ± 0.3%, 2.45 ± 0.04%, and 0.51 ± 0.05% for BDE3, BDE15, and BDE47, respectively, at the end of incubation, while mineralization rate constant was independent of the molecular structure, suggesting that solubility of LBDEs is the limit factor for their persistence in soil. The mineralization was positively linearly correlated with the formation of NERs (22.5 ± 1.9%, 11.0 ± 3.6%, and 6.7 ± 2.7% for BDE3, BDE15, and BDE47, respectively), which was mainly located in humin fraction and formed also in sterilized soil, suggesting a binding of transformation intermediates to soil humic substances and a physico-chemical entrapment of LBDEs in soil. The results provide new insights into fate of LBDE congeners in soil, and suggest a need to elucidate nature of the NERs of LBDEs, especially the stability of NERs in the environment.

The bioaccumulation, elimination, and trophic transfer of BDE-47 in the aquatic food chain of Chlorella pyrenoidosa-Daphnia magna.

As a persistent organic pollutant, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) has been widely detected in aquatic environments. However, studies on the fate and transfer of BDE-47 in the aquatic food chain remain scarce. In this study, we investigated the bioaccumulation and elimination of BDE-47 in Chlorella pyrenoidosa, as well as the trophic transfer and biomagnification of BDE-47 in the "C. pyrenoidosa-Daphnia magna" food chain, using C-14 radioactive tracer technology. After 96 h of BDE-47 exposure, the algae accumulated 88.98% ± 0.59% of the initial radioactivity from the medium, and 36.09% ± 9.22% of the accumulated residues in the algae occurred in the form of bound residues. During 96 h of elimination, only 13% ± 0.50% of accumulated radioactivity in the algae was released into the medium. After 24 h of exposure, D. magna accumulated 35.99% ± 2.55% of the initial radioactivity via water filtration from the medium, and 31.35% ± 1.92% of the accumulated radioactivity in D. magna occurred as bound residues. However, D. magna accumulated 66.89% ± 2.37% of the accumulated radioactivity in the algae via food uptake from the contaminated algae, with a high portion of radioactivity observed as bound residues (83.40% ± 0.97% of accumulated radioactivity in D. magna). This indicated a reduction in the environmental risk of BDE-47. There was obvious biomagnification in the food chain between C. pyrenoidosa and D. magna (biomagnification factors, BMFs>1), resulting in environmental hazard transfer in the aquatic food chain. However, no metabolite was found during the exposure experiment, and further studies should be carried out to investigate the intrinsic mechanisms of the trophic transfer of BDE-47, especially in multilevel food chains. Therefore, this study elucidated the effect of dietary uptake on the bioaccumulation of BDE-47 in D. magna and provided new insight for future analysis regarding the bioaccumulation and biomagnification of organic pollutants in the food chain.

Fate of 14C-bisphenol F isomers in an oxic soil and the effects of earthworm.

Bisphenol F (BPF) pollution in environment increased, but the studies on its fate and uptake in soil-earthworm systems were limited. Using 14C-tracers, environmental fate of BPF isomers in an oxic rice soil with/without earthworm Metaphire guillelmi was studied. After 59 days of incubation, mineralization increased in the order of 2,2'-BPF (18.7% ±â€¯0.3% of the initial amount) < 2,4'-BPF (21.7% ±â€¯0.2%) < 4,4'-BPF (26.9% ±â€¯0.1%). About 70% was converted to bound residues (BRs) and most of the BRs resided in the humin fraction by physical entrapment and ester-linkages. M. guillelmi decreased the mineralization and BRs of 4,4'-BPF in soil, indicating that earthworm increased the ecological risk of 4,4'-BPF. About 5.2% ±â€¯0.1% of the initial amount was accumulated in M. guillelmi and mostly in gut. Considerable amounts of the accumulated 4,4'-BPF were present as earthworm-bound residues (earthworm-BRs). The elimination of 4,4'-BPF from M. guillelmi was very slow, and there was still 96.2% of the initial accumulated radioactivity presented in earthworm after 5 days of depuration. The results of this study firstly provide the isomer - specific partitioning of three BPF isomers in an oxic soil and the uptake and depuration of 4,4'-BPF in earthworm during soil incubation.