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.

Chitosan Nanoparticles Loaded The Herbicide Paraquat: The Influence Of The Aquatic Humic Substances On The Colloidal Stability And Toxicity.

Polymeric nanoparticles have been developed for several applications, among them as carrier system of pesticides. However, few studies have investigated the fate of these materials in the environment in relation to colloidal stability and toxicity. In nature, humic substances are the main agents responsible for complexation with metals and organic compounds, as well as responsible for the dynamics of these nanoparticles in aquatic and terrestrial environments. In this context, the evaluation of the influence of aquatic humic substances (AHS) on the colloidal stability and toxicity of polymeric nanoparticles of chitosan/tripolyphosphate with or without paraquat was performed. In this study, the nanoparticles were prepared by the ionic gelation method and characterized by size distribution measurements (DLS and NTA), zeta potential, infrared and fluorescence spectroscopy. Allium cepa genotoxicity studies and ecotoxicity assays with the alga Pseudokirchneriella subcapitata were used to investigate the effect of aquatic humic substances (AHS) on the toxicity of this delivery system. No changes were observed in the physical-chemical stability of the nanoparticles due to the presence of AHS using DLS and NTA techniques. However some evidence of interaction between the nanoparticles and AHS was observed by infrared and fluorescence spectroscopies. The ecotoxicity and genotoxicity assays showed that humic substances can decrease the toxic effects of nanoparticles containing paraquat. These results are interesting because they are important for understanding the interaction of these nanostructured carrier systems with species present in aquatic ecosystems such as humic substances, and in this way, opening new perspectives for studies on the dynamics of these carrier systems in the ecosystem.

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 mu g 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. (c) 2008 Elsevier B.V. All rights reserved.

Photochemical damage and comparative performance of superoxide dismutase and ascorbate peroxidase in sugarcane leaves exposed to paraquat-induced oxidative stress

The physiological responses of sugarcane (Succharion officinarum L.) to oxidative stress induced by methyl viologen (paraquat) were examined with respect to photochemical activity, chlorophyll content, lipid peroxidation and superoxide dismutase (SOD) and ascorbate peroxidase (APX) activities. Thirty-day-old sugarcane plants were sprayed with 0, 2, 4, 6 and 8 mM methyl viologen (MV). Chlorophyll fluorescence was measured after 18 It and biochemical analyses were performed after 24 and 48 h. Concentrations of MV above 2 mM caused significant damage to photosystem II (PSII) activity. Potential and effective quantum efficiency of PSII and apparent electron transport rate were greatly reduced or practically abolished. Both chlorophyll and soluble protein contents steadily decreased with MV concentrations above 2 mM after 24 It of exposure, which became more pronounced after 48 It, achieving a 3-fold decrease. Insoluble protein contents were little affected by MV. Oxidative stress induced by MV was evidenced by increases in lipid peroxidation. Specific activity of SOD increased, even after 48 h of exposure to the highest concentrations of MV, but total activity on a fresh weight basis did not change significantly. Nondenaturing YAGE assayed with H2O2 and KCN showed that treatment with MV did not change Cu/Zn-SOD and MnSOD isoform activities. In contrast, APX specific activity increased at 2 mM MV but then dropped at higher doses. Oxidative damage induced by MV was inversely related to APX activity. It is suggested that the major MV-induced oxidative damages in sugarcane leaves were related to excess H2O2, probably in chloroplasts, caused by an imbalance between SOD and APX activities, in which APX was a limiting step. Reduced photochemical activity allowed the early detection of the ensuing oxidative stress. (c) 2007 Elsevier Inc. All rights reserved.

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.

Produtividade de feijoeiro de inverno submetido à dessecação com paraquat na pré-colheita

O conhecimento da época e da dose de aplicação de dessecante, em pré-colheita do feijoeiro, é de extrema importância para se evitarem perdas na produtividade da cultura. Diante disso, o objetivo deste trabalho foi avaliar a produtividade de feijoeiro de inverno, após aplicação do dessecante paraquat em diferentes épocas (30; 35; 40 e 45 dias após o início do florescimento - DAF) e das doses (0; 200; 400 e 600 g ha-1), em pré-colheita. O experimento foi conduzido no período de outono/inverno de 2010, em Selvíria, Mato Grosso do Sul. Os tratamentos foram dispostos em delineamento experimental de blocos ao acaso, em esquema fatorial 4 x 4 (épocas de aplicação x doses do herbicida), com quatro repetições. O aumento das doses de paraquat, até os 35 DAF, aumentou de forma linear o percentual de sementes defeituosas, enquanto as sementes tiveram sua massa reduzida linearmente, até os 40 DAF. A produtividade do feijoeiro não foi afetada pela aplicação de paraquat a partir dos 35 DAF, ao contrário do incremento da dose, que provocou redução linear desse parâmetro.

Efeito de misturas de bentazon e paraquat nas plantas daninhas e na cultura do feijão (Phaseolus vulgaris L.)

A presente pesquisa foi conduzida na Escola Superior de Agricultura "Luiz de Queiroz", em Piracicaba, SP, no ano de 1981, com o objetivo de se estudar o comportamento dos herbicidas bentazon e paraquat, aplicados isoladamente ou em misturas, em alguns cultivares de feijão e algumas espécies de plantas daninhas. Para tanto, foram instalados dois experimentos a campo, sendo um "das secas" e outro "das águas" de 1981. Os cultivares de feijão estudados foram Carioca e Moruna. Os tratamentos utilizados foram os seguintes: bentazon a 0,48 e 0,96 kg/ha; paraquat a 0,05 e 0,10 kg/ha e as misturas de tanque com 0,48 + 0,05; 0,96 + 0,10; 0,48 + +0,10 e 0,96 + 0,05 kg/ha de bentazon + paraquat, respectivamente. Foram realizadas avaliações visuais da porcentagem de injúria nos cultivares de feijão e nas espécies de plantas daninhas, sendo utilizada a fórmula de Colby para verificação dos efeitos das misturas. Os resultados mostraram que as misturas exerceram evidente efeito antagonístico nos cultivares ensaiados. Os tratamentos não influíram na produção dos cultivares Carioca e Moruna. Em solos arenosos e com baixa precipitação, o sinergismo das misturas ficou evidenciado na guanxuma (Sida glaziovii K. Sch.) e na beldroega (Portulacca oleracea L.). Em solos argilosos, com precipitação normal, os efeitos sinergísticos foram evidentes no capim-marmelada (Brachiaria plantaginea (Link.) Hitch.), capim-pé-de-galinha (Eleusine indica (L.) Gaertn.) e no apaga-fogo (Alternanthera ficoidea (L.) R. Br.).

Efectos del herbicida Paraquat sobre el zooplancton

The effects of 0.1; 0.2; 0.4 and 0.8 mlPQ/L were analized on a zooplankton community, to determine the most sensitive species and to analize the occurence of physical abnormalities. A total of 40 taxa were determined. Paraquat affected significantly the zooplankton density but not the species richness. A progressive state of deformation of these organisms was also observed. Paraquat showed to be highly toxic for the zooplankton, so this herbicide should be strictly regulated in aquatic and terrestrial ecosystems.

Ação de minhocas Eisenia foetida sobre a dissipação dos herbicidas simazina e paraquat aplicados no solo

Geralmente, os herbicidas são aplicados diretamente no solo, razão pela qual entram em contato direto com organismos deste ambiente, dentre eles as minhocas, as quais pelo metabolismo podem agir sobre resíduos desses compostos. Tomando minhocas da espécie Eisenia foetida como exemplo, determinaram-se a dissipação dos 14C-herbicidas (simazina e paraquat) e a bioacumulação destes compostos em seus tecidos, a partir de solo tratado com as concentrações recomendadas e, no caso do paraquat, também com concentrações superiores. Solo e minhocas foram analisados por extração com solventes e técnicas radiométricas, após 30 ou 90 dias de contato. As minhocas alteraram a dissipação do simazina, visto que houve 100 % de recuperação do radiocarbono na ausência de minhocas e 90 % na presença dos animais. Além disso, elas acumularam resíduos e, ou, metabólitos de simazina em seus tecidos, tendo-se detectado Fator de Bioacumulação (FB) de 1,45 e 1,17 após exposição ao solo tratado durante 30 e 90 dias, respectivamente. Por outro lado, a presença de minhocas não alterou o comportamento do herbicida paraquat aplicado ao solo, mas houve bioacumulação crescente de seus resíduos e, ou, metabólitos com o aumento da dose de tratamento (FB de 0,5; 3,2 e 5,5, respectivamente, nas concentrações recomendadas, 10 e 100 vezes superior).

Immediate and delayed effects of subchronic Paraquat exposure during an early differentiation stage in 3D-rat brain cell cultures.

Xenobiotic exposure is a risk factor in the etiology of neurodegenerative disease. It was recently hypothesized that restricted exposure during brain development could predispose for a neurodegenerative disease later in life. As neuroinflammation contributes to progressive neurodegeneration, it is suspected that neurodevelopmental xenobiotic exposure could elicit a neuroinflammatory process, which over time may assume a detrimental character. We investigated the neurotoxic effects of paraquat (PQ) in three-dimensional whole rat brain cell cultures, exposed during an early differentiation stage, comparing immediate effects-directly post exposure-with long-term effects, 20 days after interrupted PQ-administration. Adverse effects and neuroinflammatory responses were assessed by measuring changes in gene- and protein-expression as well as by determining cell morphology changes. Differentiating neural cultures were highly susceptible to PQ and showed neuronal damage and strong astrogliosis. After the 20-day washout period, neurons partially recovered, whereas astrogliosis persisted, and was accompanied by microglial activation of a neurodegenerative phenotype. Our data shows that immediate and long-term effects of subchronic PQ-exposure differ. Also, PQ-exposure during this window of extensive neuronal differentiation led to a delayed microglial activation, of a character that could promote further pro-inflammatory signals that enable prolonged inflammation, thereby fueling further neurodegeneration.

Estudo eletroanalítico do herbicida paraquat em soluções aquosas por voltametria de onda quadrada utilizando ultramicroeletrodos

The electrochemical behavior of paraquat on Pt, Au and carbon fiber ultramicroelectrodes were studied in laboratory samples by square wave voltammetry at high frequencies. The results showed two reversible peaks for paraquat reduction, in agreement to the literature data. The first peak was associated to the reduction of paraquat molecule in solution, with the further adsorption of the intermediate on the electrode surface. This adsorbed species undergoes to electroreduction in a reaction associated to the second voltammetric peak. The variation in pH and square wave parameters showed the best conditions to reduce paraquat as pH 5.0, frequency as high as 1000 s-1, scan increment of 2 mV and square wave amplitude of 50 mV. At such conditions, a variation of paraquat concentrations from 4.3 x 10-6 to 1.66 x 10-4 mol L-1 presented values for the detection limit equal to 3.9, 6.2 and 20.3 ppb on Pt, Au and carbon, respectively, at 1000 s-1. These values are quite below17 the allowed limit of paraquat in drinking water.

Aplicação de misturas de diuron com MSMA, e com paraquat, no controle de plantas daninhas de folhas largas em cultura de algodão (Gossypium hirsutum L.)

Em ensaio de campo conduzido em 1975/76 procurou-se avaliar a ação de misturas de MSMA com diuron e de paraquat com diuron, aplicadas em pós-emergência, em jato dirigido, em duas épocas diferentes, no controle de algumas plantas daninhas de folhas largas em algodão: carrapicho- do-campo (Acanthospermum australe (Loef) O. Kuntze) , falsa-poaia (Borreria ala ta (Aubl) DC), poaia-branca (Richardia brasiliensis Gomez ) e guanxuma (Sida spp) . A vegetação natural da área do ensaio era formada ainda pela gramínea capim-de-colchão (Digitaria sanguinalis (L.) Scop ). Os resultados mostraram que as misturas de 2,00 kg e 2,70 kg/ha de MSMA com, respectivamente 0,30 kg e 0,40 kg/ha de diuron, e a mistura de 0.60 kg/ha de paraquat com 0,60 kg/ ha de diuron, foram eficientes no co ntro le daquelas dicotiledôneas, e também no da gramínea. Todos os tratamentos provocaram leves sintomas de fitotoxicidade nos algodoeiros, mas desapareceram depois e não prejudicaram o desenvolvimento vegetativo das plantas, assim como a produção de algodão em caroço.

Efeitos de misturas de bentazon e paraquat no controle de plantas daninhas e na cultura do feijão (Phaseolus vulgaris L.) (nota prévia)

O objetivo da presente pesquisa foi estudar a seletividade da mistura bentazon (3-isopropil-2,1, 3-benzothiodiazinona-(4)-2,2-dióxido) com paraquat (1,1' -dimetil-4,4'-bipiridilio dicloreto) para as cultivares de feijão 'Carioca' e 'Moruna'; alêm do efeito dessa mistura no controle de algumas plantas daninhas e possíveis efeitos sinergisticos resultantes das diferentes misturas. O experimento está sendo conduzido em condições de campo na área experimental do Departamento de Agricultura e Horticultura da ESALQ em Piracicaba-SP, como tambêm em casa de vegetação. O delineamento experimental foi o de blocos ao acaso com quatro repetições. O critério de avaliação adotado foi o de "percentagem de injúria", às cultivares e às espécies de plantas daninhas, através de avaliação visual. A verificação de sinergismo foi feita utilizando-se a fórmula de Gowing citada por Colby (1). De acordo com ess e método, ve rificou -se que, para ambas as cultivares de feijão, a injúria observada foi menor que a esperada, o que caracterizou um evidente antagonismo entre as misturas desses herbicidas, em relação à cultura. Em relação ao capim-colchão (Digitaria sanguinalis (L .) Scop.) todas as misturas ensaiadas foram também antagonísticas. O sinergismo entre esses produtos ficou bastante caracterizado no controle da guanxuma (Sida glaziovii K. Sch.) e beldroega (Portulacca oleracea L.) principalmente nas doses de 0,48 + 0,05 kg/ha de bentazon + paraquat, respectivamente, notadamente ao 6.º e 8.º dia após a aplicação. Quanto ao fedegoso (Cassia tora L.) a mistura que mostrou antagonismo significativo foi 0,96 kg/ha de bentazon + 0,10 Kg/ha de paraquat.

Efeitos dos herbicidas glyphosate e paraquat, aplicados ao solo, sobre a emergência de feijão e soja e de algumas espécies daninhas

Em trabalho conduzido a campo na Estação Experimental Agronômica da UFRGS, Guaíba, RS em 1979/80, usaram-se os herbicidas glyphosate, paraquat e sua combinação, objetivando determinar os efe itos de doses e de épocas de aplicação destes herbicidas em plântulas de feijão e de soja e sobre nutrientes do solo. Pelos resultados obtidos para emergência e peso de maté ria seca da parte aé re a de soja , não houve di ferenças para os tratamentos testados. Também não ocorreram diferenças significativas à população in ic ia l de feijão e sobre os elementos de solo analisados (Ca, Mg e K). Com relação ao peso de matéria seca da parte aérea do feijão, verificou-se que houve interação entre herbicida e doses usadas, tendo glyphosate isolado e glyphosate mais paraquat aplicados seqüencialmente nas doses máximas causado redução significativa naquele parâmetro. Com relação ao paraquat, não foram detectadas diferenças significativas entre as doses testadas.