RESUMO
2,4-Dinitroanisole (DNAN) is an insensitive munitions compound expected to replace 2,4,6-trinitrotoluene (TNT). The product of DNAN's reduction in the environment is 2,4-diaminoanisole (DAAN), a toxic and carcinogenic aromatic amine. DAAN is known to become irreversibly incorporated into soil natural organic matter (NOM) after DNAN's reduction. Herein, we investigate the reactions between DAAN and NOM under anoxic conditions, using 1,4-benzoquinone (BQ) and methoxybenzoquinone (MBQ) as model humic moieties of NOM. A new method stopped the fast reactions between DAAN and quinones, capturing the fleeting intermediates. We observed that DAAN incorporation into NOM (represented by BQ and MBQ models) is quinone-dependent and occurs via Michael addition, imine (Schiff-base) formation, and azo bond formation. After dimers are formed, incorporation reactions continue, resulting in trimers and tetramers. After 20 days, 56.4% of dissolved organic carbon from a mixture of DAAN (1 mM) and MBQ (3 mM) had precipitated, indicating an extensive polymerization, with DAAN becoming incorporated into high-molecular-weight humic-like compounds. The present work suggests a new approach for DNAN environmental remediation, in which DNAN anaerobic transformation can be coupled to the formation of non-extractable bound DAAN residues in soil organic matter. This process does not require aerobic conditions nor a specific catalyst.
RESUMO
Pharmaceutical active compounds (PhACs) are environmentally ubiquitous around the world, and the countries of Latin America (LATAM) are not the exception; however there is still little knowledge of the magnitude and conditions of their occurrence in LATAM and of the environmental consequences of their presence. The present work reviews 79 documents published from 2007 to 2019 on the occurrence, concentrations, and sources of PhACs and hormones in surface water (SW), wastewater (WW), and treated wastewater (TWW) in LATAM and on the circumstances of their release to the environment. Research efforts are reported in only ten countries and confirm the presence of 159 PhACs, mainly analgesics and anti-inflammatories, although extraordinarily high concentrations of carbamazepine (830 µg/L) and ethinylestradiol (6.8 µg/L) were found in Ecuador and Brazil, respectively. The analysis of maximum concentrations and the ecotoxicological risk assessment corroborate that (1) these values exceed the environmental concentrations found in other parts of the world, (2) the environmental risk posed by these concentrations is remarkably high, and (3) there is no statistically significant difference between the maximum concentrations found in WW and those found in TWW. The main source of PhACs in LATAM's aquatic environment is WW; hence, these countries should direct substantial efforts to develop efficient and cost-effective treatment technologies and plan and apply WW management strategies and regulations. This analysis presents the current states of occurrence, concentrations, and sources of PhACs in the aquatic environment of LATAM and outlines the magnitude of the environmental problem in that part of the world.