RESUMO

Multiple anthropogenic stressors act simultaneously on the environment, with consequences different from those caused by single-stressor exposure. We investigated how the combination of the invasive mussel Limnoperna fortunei and a widely applied herbicide, Roundup Max®, affected freshwater microscopic communities and water quality. Further, we compared these results with those induced by the combination of the mussel and technical-grade glyphosate. We carried out a 34-day experiment in outdoor mesocosms, applying the following six treatments: 6 mg L(-1) of technical-grade glyphosate (G), the equivalent concentration of glyphosate in Roundup Max® (R), 100 mussels (M), the combination of mussels and herbicide either in the technical-grade or formulated form (MG and MR, respectively), and control (C). Herbicides significantly increased total phosphorus in water; R and MR showed greater initial total nitrogen and ammonium. R increased picoplankton abundance and caused an eightfold increase in phytoplankton, with high turbidity values; G had a lower effect on these variables. Herbicide-mussel combination induced an accelerated dissipation of glyphosate in water (MG 6.36 ± 0.83 mg G g DW(-1) day(-1) and MR 5.16 ± 1.26 mg G g DW(-1) day(-1)). A synergistic effect on ammonium was observed in MR but not in MG. MR and MG had an antagonistic effect on phytoplankton, which showed a drastic reduction due to grazing, as revealed by M. We provide evidence of differential effects of Roundup Max® and technical-grade glyphosate over water quality and microscopic communities, and in combination with mussels. However, in the combination of mussels and herbicides, mussels seem to play a leading role. In the presence of L. fortunei, the effects of higher nutrient availability provided by herbicides addition were counteracted by the filtration activity of mussels, which released nutrients, grazed on picoplankton and phytoplankton, and boosted the development of other primary producers, periphyton and metaphyton.

Assuntos

RESUMO

Since it was commercially introduced in 1974, glyphosate has been one of the most commonly used herbicides in agriculture worldwide, and there is growing concern about its adverse effects on the environment. Assuming that glyphosate may increase the organic turbidity of water bodies, we evaluated the effect of a single application of 2.4 ± 0.1 mg l(-1) of glyphosate (technical grade) on freshwater bacterioplankton and phytoplankton (pico, micro, and nanophytoplankton) and on the physical and chemical properties of the water. We used outdoor experimental mesocosms under clear and oligotrophic (phytoplanktonic chlorophyll a = 2.04 µg l(-1); turbidity = 2.0 NTU) and organic turbid and eutrophic (phytoplanktonic chlorophyll a = 50.3 µg l(-1); turbidity = 16.0 NTU) scenarios. Samplings were conducted at the beginning of the experiment and at 1, 8, 19, and 33 days after glyphosate addition. For both typologies, the herbicide affected the abiotic water properties (with a marked increase in total phosphorus), but it did not affect the structure of micro and nanophytoplankton. In clear waters, glyphosate treatment induced a trend toward higher bacteria and picoeukaryotes abundances, while there was a 2 to 2.5-fold increase in picocyanobacteria number. In turbid waters, without picoeukaryotes at the beginning of the experiment, glyphosate decreased bacteria abundance but increased the number of picocyanobacteria, suggesting a direct favorable effect. Moreover, our results show that the impact of the herbicide was observed in microorganisms from both oligo and eutrophic conditions, indicating that the impact would be independent of the trophic status of the water body.

Assuntos

RESUMO

Glyphosate [N-phosphono-methylglycine (PMG)] is the most used herbicide worldwide, particularly since the development of transgenic glyphosate-resistant (GR) crops. Aminomethylphosphonic acid (AMPA) is the main glyphosate metabolite, and it may be responsible for GR crop damage upon PMG application. PMG degradation into AMPA has hitherto been reckoned mainly as a biological process, produced by soil microorganisms (bacteria and fungi) and plants. In this work, we use density functional calculations to identify the vibrational bands of PMG and AMPA in surface-enhanced Raman spectroscopy (SERS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra experiments. SERS shows the presence of AMPA after glyphosate is deposited from aqueous solution on different metallic surfaces. AMPA is also detected in ATR-FTIR experiments when PMG interacts with metallic ions in aqueous solution. These results reveal an abiotic degradation process of glyphosate into AMPA, where metals play a crucial role.

Assuntos

RESUMO

Glyphosate is a non-selective, broad spectrum, post-emergent herbicide widely used in weed control. Aminomethylphosphonic acid (AMPA) is one of the main products of biodegradation of glyphosate in natural systems before its ultimate mineralization and also the breakdown product of more complex phosphonates such as nitrilotris-(methylenephosphonic acid). The adsorption isotherms and surface coverage of AMPA and glyphosate (N-phosphomethylglycine, PMG) in aqueous suspensions of goethite as a function of pH were measured. Electrophoretic mobility curves forthe PMG/goethite system were also determined. The ATR-FTIR interfacial spectra of the surface complexes of AMPA and PMG onto goethite were analyzed as a function of the pH and the surface coverage. The phosphonate moiety of these two ligands coordinates to the iron oxide surface with similar structures as the methylphosphonic acid despite the presence of the amino and/or carboxylate groups of their molecules. Two predominating complexes have been identified where the phosphonate group in PMG or AMPA bonds monodentately or bridges bidentately to the surface of iron oxide in an inner sphere mode, while the carboxylate and amino group are noncoordinated to the surface. The stability constants of the surface complexes (triple bond)FeO-P(O)(OH)--R, (triple bond)FeO--P(O)2--R, and ((triple bond)FeO)2--P(O)--R were calculated using the constant capacitance model.

Assuntos

Assuntos

RESUMO

The cyclization of ethyl 2-(aminosulfonyl)benzoate (ASB) to give saccharin was investigated in aqueous solutions at pH between 5.2 and 9.5 and in the temperature range of 296.2-334.2 K. The initial concentration of the reactant was varied between 1.45 x 10(-5) and 3.86 x 10(-4) M. Ultraviolet spectroscopy was used to obtain the kinetic data. The reaction is acid catalyzed and follows pseudo-first-order kinetics. The experimental rate constant, k(obs), increases with temperature and pH. Its dependence on the temperature and pH is well described by: k(obs) = k1 [OH-] = [(2.52 +/- 0.9) x 10(16) exp(-20.2 +/- 1 kcalmol(-1)/RT) s(-1)][OH-] A mechanism is proposed and the half-life of ethyl ASB is calculated.

Assuntos