Paraquat degradation by photocatalysis: experimental desing and optimization.

This study describes the experimental design and optimization of application TiO2 catalysts doped with 0.5, 1, 1.5, 2.0% of Fe. The catalysts were prepared using the impregnation method applied in Paraquat herbicide degradation. The catalysts were characterized by the following techniques: specific surface area and volume, mean pore diameter (BET method), scanning electron microscopy and photoacoustic spectroscopy. The characterization presented results indicating that both calcination temperature and the increase nominal metallic load affected by the structure of catalysts, changing the textural properties, as well as the band gap. The catalyst that presented the best herbicide removal percentage was TiO2 calcined at 773 K with removal of 90.2%. However, according to the experimental design and optimization, both variables (calcination temperature and Fe percentage) are significant in the process. In addition, a positive effect was found in the interaction between the two variables. The values show that a third order kinetic model better described the Paraquat photocatalytic degradation.

Modeling, kinetic, and equilibrium characterization of paraquat adsorption onto polyurethane foam using the ion-pairing technique.

We studied the adsorption of paraquat onto polyurethane foam (PUF) when it was in a medium containing sodium dodecylsulfate (SDS). The adsorption efficiency was dependent on the concentration of SDS in solution, because the formation of an ion-associate between the cationic paraquat and the dodecylsulfate anion was found to be a fundamental step in the process. A computational study was carried out to identify the possible structure of the ion-associate in aqueous medium. The obtained data demonstrated that the structure is probably formed from four units of dodecylsulfate bonded to one paraquat moiety. The results showed that 94% of the paraquat present in 45 mL of a solution containing 3.90 × 10(-5) mol L(-1) could be retained by 300 mg of PUF, resulting in the removal of 2.20 mg of paraquat. The experimental data were reasonably adjusted to the Freundlich isotherm and to the pseudo-second-order kinetic model. Also, the application of Morris-Weber and Reichenberg models indicated that both film-diffusion and intraparticle-diffusion processes were active during the control of the adsorption kinetics.

Synthesis and characterization of TiO2 and TiO2/Ag for use in photodegradation of methylviologen, with kinetic study by laser flash photolysis.

This paper reports the synthesis, characterization, and application of TiO2 and TiO2/Ag nanoparticles for use in photocatalysis, employing the herbicide methylviologen (MV) as a substrate for photocatalytic activity testing. At suitable metal to oxide ratios, increases in silver surface coating on TiO2 enhanced the efficiency of heterogeneous photocatalysis by increasing the electron transfer constant. The sol-gel method was used for TiO2 synthesis. P25 TiO2 was the control material. Both oxides were subjected to the same silver incorporation process. The materials were characterized by conventional spectroscopy, SEM micrography, X-ray diffraction, calculation of surface area per mass of catalyst, and thermogravimetry. Also, electron transfers between TiO2 or TiO2/Ag and MV in the absence and presence of sodium formate were investigated using laser flash photolysis. Oxides synthesized with 2.0 % silver exhibited superior photocatalytic activity for MV degradation.

Chitosan/tripolyphosphate nanoparticles loaded with paraquat herbicide: an environmentally safer alternative for weed control.

Paraquat is a fast acting nonselective contact herbicide that is extensively used worldwide. However, the aqueous solubility and soil sorption of this compound can cause problems of toxicity in nontarget organisms. This work investigates the preparation and characterization of nanoparticles composed of chitosan and sodium tripolyphosphate (TPP) to produce an efficient herbicidal formulation that was less toxic and could be used for safer control of weeds in agriculture. The toxicities of the formulations were evaluated using cell culture viability assays and the Allium cepa chromosome aberration test. The herbicidal activity was investigated in cultivations of maize (Zea mays) and mustard (Brassica sp.), and soil sorption of the nanoencapsulated herbicide was measured. The efficiency association of paraquat with the nanoparticles was 62.6 ± 0.7%. Encapsulation of the herbicide resulted in changes in its diffusion and release as well as its sorption by soil. Cytotoxicity and genotoxicity assays showed that the nanoencapsulated herbicide was less toxic than the pure compound, indicating its potential to control weeds while at the same time reducing environmental impacts. Measurements of herbicidal activity showed that the effectiveness of paraquat was preserved after encapsulation. It was concluded that the encapsulation of paraquat in nanoparticles can provide a useful means of reducing adverse impacts on human health and the environment, and that the formulation therefore has potential for use in agriculture.

New insights into antioxidant strategies against paraquat toxicity.

Paraquat (PQ, 1,1'-dimethyl-4-4'-bipyridinium dichloride) is a highly toxic quaternary ammonium herbicide widely used in agriculture, it exerts its toxic effects mainly because of its redox cycle through the production of superoxide anions in organisms, leading to an imbalance in the redox state of the cell causing oxidative damage and finally cell death. The contribution of mitochondrial dysfunction including increased production of reactive oxygen species besides the reduction in oxygen consumption as well as in the activity of some respiratory complexes has emerged as a key component in the mechanisms through which PQ induces cell death. Although several aspects of PQ-mitochondria interaction remain to be clarified, recent advances have been conducted with reproducible results. Currently, there is no treatment for PQ poisoning; however, several studies taking into account oxidative stress as the main mechanism of PQ-induced toxicity suggest an antioxidant therapy as a viable alternative. In fact, it has been shown that the antioxidants naringin, sylimarin, edaravone, Bathysa cuspidata extracts, alpha-lipoic acid, pirfenidone, lysine acetylsalicylate, selenium, quercetin, C-phycocyanin, bacosides, and vitamin C may be useful in the treatment against PQ toxicity. The main mechanisms involved in the protective effect of these antioxidants include the reduction of oxidative stress and inflammation and the induction of antioxidant defenses. Interestingly, recent findings suggest that the induction of nuclear factor erythroid like-2 (Nrf2), a major regulator of the antioxidant response, by some of the above-mentioned antioxidants, has been involved in the protective effect against PQ-induced toxicity.

Reactivity of iron(II)-bound nitrosyl hydride (HNO, nitroxyl) in aqueous solution.

The reactivity of coordinated nitroxyl (HNO) has been explored with the [Fe(II)(CN)(5)HNO](3-) complex in aqueous medium, pH 6. We discuss essential biorelevant issues as the thermal and photochemical decompositions, the reactivity toward HNO dissociation, the electrochemical behavior, and the reactions with oxidizing and reducing agents. The spontaneous decomposition in the absence of light yielded a two-electron oxidized species, the nitroprusside anion, [Fe(II)(CN)(5)NO](2-), and a negligible quantity of N(2)O, with k(obs)≈5×10(-7)s(-1), at 25.0°C. The value of k(obs) represents an upper limit for HNO release, comparable to values reported for other structurally related L ligands in the [Fe(II)(CN)(5)L](n-) series. These results reveal that the FeN bond is strong, suggesting a significant σ-π interaction, as already postulated for other HNO-complexes. The [Fe(II)(CN)(5)HNO](3-) ion showed a quasi-reversible oxidation wave at 0.32 V (vs normal hydrogen electrode), corresponding to the [Fe(II)(CN)(5)HNO](3-)/[Fe(II)(CN)(5)NO](3-),H(+) redox couple. Hexacyanoferrate(III), methylviologen and the nitroprusside ion have been selected as potential oxidants. Only the first reactant achieved a complete oxidation process, initiated by a proton-coupled electron transfer reaction at the HNO ligand, with nitroprusside as a final oxidation product. Dithionite acted as a reductant of [Fe(II)(CN)(5)HNO](3-), in a 4-electron process, giving NH(3). The high stability of bound HNO may resemble the properties in related Fe(II) centers of redox active enzymes. The very minor release of N(2)O shows that the redox conversions may evolve without disruption of the FeN bonds, under competitive conditions with the dissociation of HNO.

Paraquat-loaded alginate/chitosan nanoparticles: preparation, characterization and soil sorption studies.

Agrochemicals are amongst the contaminants most widely encountered in surface and subterranean hydrological systems. They comprise a variety of molecules, with properties that confer differing degrees of persistence and mobility in the environment, as well as different toxic, carcinogenic, mutagenic and teratogenic potentials, which can affect non-target organisms including man. In this work, alginate/chitosan nanoparticles were prepared as a carrier system for the herbicide paraquat. The preparation and physico-chemical characterization of the nanoparticles was followed by evaluation of zeta potential, pH, size and polydispersion. The techniques employed included transmission electron microscopy, differential scanning calorimetry and Fourier transform infrared spectroscopy. The formulation presented a size distribution of 635 ± 12 nm, polydispersion of 0.518, zeta potential of -22.8 ± 2.3 mV and association efficiency of 74.2%. There were significant differences between the release profiles of free paraquat and the herbicide associated with the alginate/chitosan nanoparticles. Tests showed that soil sorption of paraquat, either free or associated with the nanoparticles, was dependent on the quantity of organic matter present. The results presented in this work show that association of paraquat with alginate/chitosan nanoparticles alters the release profile of the herbicide, as well as its interaction with the soil, indicating that this system could be an effective means of reducing negative impacts caused by paraquat.

Degradation of the herbicides clomazone, paraquat, and glyphosate by thermally activated peroxydisulfate.

Activated sodium peroxydisulfate has the potential to in situ destruct many organic contaminants because of the generation of the stronger oxidant sulfate radical. From photochemical activation of peroxydisulfate in flash-photolysis experiments, the bimolecular rate constants for the reaction of sulfate radical with glyphosate (1.6 × 10(8) M(-1) s(-1)) and paraquat (1.2 × 10(9) M(-1) s(-1)) at 25 °C were obtained. Thermal activation of peroxydisulfate was shown to degrade the herbicides clomazone, paraquat, and glyphosate. Although the herbicide degradation was observed to take place in less than 1 h, the mineralization of the organic carbon required longer reaction times, because of the formation of stable organic intermediates. For similar initial total organic carbon (TOC) values, TOC profiles were similar for experiments with different substrates (the herbicides, humic acids, and a mixture of glyphosate and humic acids), which indicates that the mineralization of all of the samples is limited by the production of SO(4)(•) (-) radicals. A linear correlation between the initial amount of SO(4)(•) (-) needed per mole of C and the average oxidation state was found.

Enzymatic-spectrophotometric determination of paraquat in urine samples: a method based on its toxic mechanism.

Paraquat is a broad-spectrum contact herbicide that has been encountered worldwide in several cases of accidental, homicidal, and suicidal poisonings. The pulmonary toxicity of this compound is related to the depletion of NADPH in the pneumocytes, which is continuously consumed by the reduction/oxidation of paraquat and reductase enzyme systems in the presence of O(2) (redox cycling). Based on this mechanism, an enzymatic-spectrophotometric method was developed for the determination of paraquat in urine samples. The velocity of NADPH consumption was monitored at 340 nm, every 10 s during 15 min. The velocity of NADPH oxidation correlated with the paraquat levels found in samples. The enzymatic-spectrophotometric method showed to be sensitive, making possible the detection of paraquat in urine samples at concentrations as low as 0.05 mg/L.

A multicommuted flow system with solenoid micro-pumps for paraquat determination in natural waters.

A flow system designed with solenoid micro-pumps is proposed for the determination of paraquat in natural waters. The procedure involves the reaction of paraquat with dehydroascorbic acid followed by spectrophotometric measurements. The proposed procedure minimizes the main drawbacks related to the standard chromatographic procedure and to flow analysis and manual methods with spectrophotometric detection based on the reaction with sodium dithionite, i.e. high solvent consumption and waste generation and low sampling rate for chromatography and high instability of the reagent in the spectrophotometric procedures. A home-made 10-cm optical-path flow cell was employed for improving sensitivity and detection limit. Linear response was observed for paraquat concentrations in the range 0.10-5.0 mg L(-1). The detection limit (99.7% confidence level), sampling rate and coefficient of variation (n=10) were estimated as 22 microg L(-1), 63 measurements per hour and 1.0%, respectively. Results of determination of paraquat in natural water samples were in agreement with those achieved by the chromatographic reference procedure at the 95% confidence level.

Gas chromatographic-mass spectrometric method for the determination of the herbicides paraquat and diquat in plasma and urine samples.

In the present work, a method was developed and optimized aiming to determinate the herbicides paraquat (PQ) and diquat (DQ) in human plasma and urine samples. An initial procedure of chemical reduction of the analytes by adding NaBH4 directly in the buffered samples (pH 8.0) was performed. This procedure was necessary to convert the quaternary ammonium substances into more volatile compounds for gas chromatographic analysis. The reduction compounds were extracted with C18 cartridges (solid-phase extraction). Ethyl paraquat (EPQ) was used as internal standard (IS). Gas chromatography-mass spectrometry (GC-MS) was used to identify and quantify the analytes in selected ion monitoring (SIM) mode. The limits of detection were 0.05 mg/l for both PQ and DQ. By using the weighted least squares linear regression (1/x1/2 for plasma and 1/y for urine), the accuracy of the analytical method was improved at the lower end of the calibration curve (from 0.1 to 50 mg/l; r>0.98). This method can be readily utilized as an important tool to confirm the suspicion of PQ and/or DQ poisoning and evaluate the extent of the intoxication.

Intoxicación por paraquat: toxicidad sistémica después de exposición cutánea / Paraquat poisoning: systemic toxicity after dermal exposure

La ingestión del Paraquat (dicloruro de 1,1 dimetil-4,4 dipiridilio) es el caso más común de la intoxicación fatal por plaguicidas, pero no se debe descartar la posibilidad de otras vías que lleven a un daño multiorgánico, como es el caso de la absorción dérmica del Paraquat. Nosotros reportamos el caso de un agricultor quien desarrollo daño renal y hepático después de una exposición aguda de la piel escrotal con el herbicida Paraquat con recuperación eventual del paciente. Este caso demuestra que la exposición dérmica por Paraquat, especialmente del escroto, puede producir seria toxicidad sistémica; siendo el primer caso reportado en 5 años en nuestro Instituto de toxicidad sistémica por contacto cutáneo de este químico. Se debe tomar estricta precaución, incluyendo el uso de ropa protectora siempre que se va a usar este químico.

Paraquat: as implicações do uso inadequado de um herbicida seguro / Paraquat: the implications of improper use of a herbicide insurance

Dentre os mais importantes compostos agrotóxicos encontram-se os herbicidas por causa do seu volume de utilização. Não se pode substituí-los com métodos não químicos que são mais laborosos ou de custo mais elevado. Esta situação é uma importante razão pela qual a agricultura orgânica em larga escala foi mal projetada desde o princípio. As intoxicações por Paraquat são sempre consideradas graves e ingestões de quantidades superiores a 50ml tem prognósticos sombrios. Os acidentes com este veneno são subestimados em nosso Estado por causa da falta de uma adequada notificação e contabilização dos casos ocorridos. As tentativas de suicídio com este composto deixaram de ser raras e passam a configurar rotinas nos hospitais do interior. No Estado do Rio de Janeiro, a cidade de Nova Friburgo é a que tem notificado mais casos aos Centros de Controle de Intoxicações. As tentativas de suicídio superam o número de casos de intoxicações acidentais. Geralmente os suicidas são trabalhadores rurais com acesso ao produto. Sendo assim, a problemática da utilização do paraquat na agricultura ultrapassa a da indequada manipulação e manejo do produto nas lavouras atingindo o mérito do desvio do uso regular do herbicida, o que configura numa visão mais abrangente, um importante problema de saúde pública e por que não dizer, ocupacional.

Paraquat / Paraquat

Atualmente com os avanços tecnológicos e a diversidade de substâncias químicas em desenvolvimento, a preocupação com o impacto ambiental e a saúde dos seres humanos tem sido motivo de muitos debates. Para assegurar a efetividade dos direitos ambientais e a Constituição ditou como controlar, comercializar e empregar técnicas e métodos para substâncias que comportem risco para vida, qualidade de vida e meio ambiente. Dentre os agrotóxicos utilizados no Brasil, destaca-se o uso do herbicida Paraquat que é um dos efetivos herbicidas existentes e também um dos maiores venenos do mundo. Os efeitos do Paraquat se notam nos ambientes aquáticos, nas plantas, nos seres vivos e principalmente no homem. Felizmente é fácilmente degradada através da luz solar, luz ultra-violeta e microorgansimos existentes no solo. A toxicidade aguda de Paraquat é extrema. Uma colher de chá é dose letal para um homem adulto. Paraquat tem se mostrado tóxico aos seres humanos em todas as formas de exposição quer sejam inalatória, cutânea ou oral. Praticamente todos os sistemas são afetados após a exposição ao Paraquat: pele, sistema renal, sistema gastrointestinal, hepático, sistema cardiovascular, sistema nervoso central, glândula adrenal, sistema hematológico, sistema músculo esquelético, sistema imunológico. O principal meio de exposição dos trabalhadores é por via inalatória e cutânea. Todas as exposições requerem hospitalização e devem ser tratadas como envenenamento potencialmente fatal. A morte resulta de lesão pulmonar após semanas de ingestão. Se grandes quantidades forem ingeridas (como em casos de suicídio) a morte irá ocorrer em poucos dias com vários órgãos vitais comprometidos.