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1.
Sci Total Environ ; 774: 145060, 2021 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-33609836

RESUMO

An analytical method based on liquid chromatography coupled to mass spectrometry was validated to quantify five perfluorinated carboxylic acids (PFCA) namely, perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), and perfluoroundecanoic acid (PFUnA), in wastewater produced in a megacity. Sampling was performed on a monthly basis, obtaining samples from the undergrounded sewerage system and the main open-air canal transporting wastewater out the city. Steady levels of the sum of the target PFCA (Æ©PFCA) were determined on both sites through the study: 419.4 ± 24.3 ng L-1 in undergrounded sewage and 591.1 ± 39 ng L-1 in the open-air canal. Short-chain PFCA (PFBA, PFHxA, and PFHpA) were abundant, while concentrations of PFOA and PFUnA remained lower in both sampling sites. The open-air canal was transected in four sampling points, which were sampled throughout the monitoring campaign, finding that furtive discharges of municipal and industrial wastewater increased the levels of short-chain PFCA, while those of PFOA and PFUnA were depleted. Relevant concentrations of PFBA (176.9 ± 3.3 ng L-1), PFHxA (133.4 ± 2.5 ng L-1), PFHpA (116.6 ± 3.9 ng L-1), PFOA (133.1 ± 3.5 ng L-1), and PFUnA (23.5 ± 6.5 ng L-1) were found 60 km downstream, where the wastewater transported by the open-air canal is used in irrigation. A fraction of sewage is treated in a conventional wastewater treatment plant. The concentration of short-chain PFCA increased in effluent, adding extra loads of PFBA, PFHxA, and PFHpA to the environment.

2.
Life Sci Space Res (Amst) ; 22: 125-136, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31421844

RESUMO

Nitrates and perchlorates are present both on Earth and Mars. In the Martian environment perchlorates dominate over nitrates whereas on Earth is contrariwise. This implies that the mechanisms responsible for their formation are different for both planets. The chemical elements required for their formation are nitrogen and chlorine, which are present in the atmosphere and surface, respectively. Dust in the Martian atmosphere causes atmospheric perturbations that lead to the development of dust-devils and sandstorms. Dust devils contain both chemical elements simultaneously, and normally generate high electric fields that can trigger the formation of electric discharges. Here we present laboratory experiments of this phenomenon using laser ablation of a sodium chloride (NaCl) plate in two different simulated atmospheres: (1) 96% CO2, 2% N2 and 2% Ar; and (2) 66% CO2, 33% N2 and 1% Ar. The dust that condensed and accumulated on the walls of the reactor was analyzed by different analytical techniques that included Fourier transform infrared spectroscopy, visible spectroscopy using azo dyes, thermogravimetry/simultaneous thermal analyses coupled to mass spectrometry, powder X-ray diffraction, and ion chromatography. The main components of the ablated dust corresponded to NaCl ≥ 91.5%, sodium nitrate (NaNO3 = 1.6-6.0%), and sodium perchlorate (NaClO4 âˆ¼ 0.2-0.3%). It is interesting to note that these salts formed in a dry process that is relevant to Mars today. A thermochemical model was used to understand the chemical steps that led to the formation of these salts in the gas phase. The NaNO3NaClO4 (wt/wt) ratio of this process was estimated to vary from 5.0 to 30.0; this ratio is too high compared to that found on Mars (NO3-ClO4- (wt/wt)) from 0.004 to 0.13). This implies that gaseous NaCl was not efficiently oxidized to perchlorate by the electric discharge process. We propose instead that gaseous metal chlorides (e.g., MgCl2, NaCl, CaCl2, KCl) were supplied to the atmosphere by the volatilization of chloride minerals present in the dust by electric discharges generated in dust devils and were subsequently oxidized to perchlorate by photochemical processes. Further work is required to assess the relative contribution of this possible source.


Assuntos
Atmosfera/química , Marte , Nitratos/química , Percloratos/química , Poeira , Meio Ambiente Extraterreno , Simulação de Ambiente Espacial , Eletricidade Estática
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