RESUMEN
Polyoxyethylene tallow amine (POE-T) is a member of the polyoxyethylene alkylamine (POEA) class of nonionic surfactants and is a component of some glyphosate-based formulations. The presence of POE-T improves foliar uptake of glyphosate in weeds, thereby reducing the amount of glyphosate needed for weed control. To further characterize the environmental fate of POE-T, aerobic soil degradation, hydrolysis, adsorption/desorption, and aerobic aquatic degradation studies were conducted according to U.S. EPA and OECD pesticide regulatory testing guidelines. POE-T labeled with carbon-14 was used in the studies to aid in analysis, assess mineralization to CO2, and allow for mass balance determinations. The aerobic soil half-lives (DT50) for POE-T ranged from 20 to 166 days with DT50 values increasing with increasing soil percent organic carbon (OC). POE-T was hydrolytically stable at pH 4-9. POE-T adsorbed strongly to soil (KFocads = 17,600-114,000) with sorption generally increasing as soil percent OC increased. The aerobic aquatic (water-sediment) system DT50s for POE-T were 14-29 days, with POE-T dissipating from the water column with DT50s of 0.10-0.12 days through metabolism and adsorption to sediment. Based on these results, aquatic organisms are unlikely to be exposed to POE -T in the water column for more than a few hours following waterborne exposure and sediment is a significant sink for POE-T in aquatic systems. However, bioavailability of POE-T in sediment and soil is predicted to be low based on strong adsorption and it is not readily desorbed.
Asunto(s)
Herbicidas , Polietilenglicoles , Aminas/química , Radioisótopos de Carbono , Exposición a Riesgos Ambientales , Grasas , Herbicidas/química , Polietilenglicoles/química , Medición de RiesgoRESUMEN
Roundup® branded herbicides contain glyphosate, a surfactant system and water. One of the surfactants used is polyethoxylated tallow amine (POE-T). A toxicology dataset has been developed to derive the most representative points of departure for human health risk assessments. Concentrated POE-T was very irritating to skin, corrosive to eyes, and sensitizing to skin. The irritation and sensitization potential of POE-T diminishes significantly upon dilution with water. Repeated dosing of rats with POE-T produced gastrointestinal effects but no systemic effect on organ systems. POE-T was not genotoxic and had no effect on embryo-fetal development or reproduction. The occupational risk assessment of POE- T for the agricultural use of glyphosate products has demonstrated that margins of exposure (MOEs) are 2517 and 100,000 for maximum and geometric mean dermal exposures, respectively. In the food risk assessment for relevant agricultural uses, the range of MOEs for consumption of foods from plant and animal origin were 330 to 2909. MOEs ≥100 are generally considered to be of no toxicological concern. Based on the results of the occupational and food risk assessments, it is concluded that there are no significant human health issues associated with the use of POE-T as a surfactant in glyphosate products.
Asunto(s)
Aminas/toxicidad , Grasas/toxicidad , Irritantes/toxicidad , Polietilenglicoles/toxicidad , Tensoactivos/toxicidad , Administración por Inhalación , Administración Oral , Animales , Exposición Dietética , Perros , Contaminación de Alimentos , Glicina/análogos & derivados , Cobayas , Herbicidas , Humanos , Exposición por Inhalación , Ratones , Conejos , Ratas , GlifosatoAsunto(s)
Ecología , Glicina , Quelantes , Glicina/análogos & derivados , Medición de Riesgo , GlifosatoRESUMEN
Essential nutrients such as trace metal ions, amino acids, and sugars are transported in the phloem from leaves to other parts of the plant. The major chelating agents in phloem include nicotianamine, histidine, cysteine, glutamic acid, and citrate. A computer model for the speciation of metal ions in phloem has been used to assess the degree to which the widely used herbicide glyphosate binds to Fe(3+), Fe(2+), Cu(2+), Zn(2+), Mn(2+), Ca(2+), and Mg(2+) in this fluid over the pH range of 8 to 6.5. The calculations show that glyphosate is largely unable to compete effectively with the biological chelating agents in phloem. At a typical phloem pH of 8, 1.5 mM glyphosate binds 8.4% of the total Fe(3+), 3.4% of the total Mn(2+), and 2.3% of the total Mg(2+) but has almost no effect on the speciation of Ca(2+), Cu(2+), Zn(2+), and Fe(2+). As the pH decreases to 6.5, there are some major shifts of the metal ions among the biological chelators, but only modest increases in glyphosate binding to 6% for Fe(2+) and 2% for Zn(2+). The calculations also indicate that over 90% of the glyphosate in phloem is not bound to any metal ion and that none of the metal-glyphosate complexes exceed their solubility limits.
Asunto(s)
Quelantes/metabolismo , Simulación por Computador , Glicina/análogos & derivados , Herbicidas/química , Metales/metabolismo , Floema/química , Cationes , Glicina/metabolismo , Concentración de Iones de Hidrógeno , Solubilidad , GlifosatoRESUMEN
CONTEXT: The case fatality from acute poisoning with glyphosate-containing herbicides is approximately 7.7% from the available studies but these have major limitations. Large prospective studies of patients with self-poisoning from known formulations who present to primary or secondary hospitals are needed to better describe the outcome from acute poisoning with glyphosate-containing herbicides. Furthermore, the clinical utility of the glyphosate plasma concentration for predicting clinical outcomes and guiding treatment has not been determined. OBJECTIVE: To describe the clinical outcomes, dose-response, and glyphosate kinetics following self-poisoning with glyphosate-containing herbicides. METHODS: This prospective observational case series was conducted in two hospitals in Sri Lanka between 2002 and 2007. We included patients with a history of acute poisoning. Clinical observations were recorded until discharge or death. During a specified time period, we collected admission (n = 216, including five deaths) and serial (n = 26) blood samples in patients. Severity of poisoning was graded using simple clinical criteria. RESULTS: Six hundred one patients were identified; the majority ingested a concentrated formulation (36%, w/v glyphosate). Twenty-seven percent were asymptomatic, 63.7% had minor poisoning, and 5.5% of patients had moderate to severe poisoning. There were 19 deaths (case fatality 3.2%) with a median time to death of 20 h. Gastrointestinal symptoms, respiratory distress, hypotension, altered level of consciousness, and oliguria were observed in fatal cases. Death was strongly associated with greater age, larger ingestions, and high plasma glyphosate concentrations on admission (>734 microg/mL). The apparent elimination half-life of glyphosate was 3.1 h (95% CI = 2.7-3.6 h). CONCLUSIONS: Despite treatment in rural hospitals with limited resources, the mortality was 3.2%, which is lower than that reported in previous case series. More research is required to define the mechanism of toxicity, better predict the small group at risk of death, and find effective treatments.
Asunto(s)
Glicina/análogos & derivados , Herbicidas/envenenamiento , Intento de Suicidio/estadística & datos numéricos , Suicidio/estadística & datos numéricos , Adolescente , Adulto , Factores de Edad , Femenino , Glicina/farmacocinética , Glicina/envenenamiento , Semivida , Herbicidas/química , Humanos , Masculino , Persona de Mediana Edad , Pronóstico , Estudios Prospectivos , Factores de Riesgo , Servicios de Salud Rural , Índice de Severidad de la Enfermedad , Sri Lanka , Adulto Joven , GlifosatoRESUMEN
The chlorination reactions of glyphosate and glycine in water were thoroughly studied. Utilizing isotopically enriched (13C and 15N) samples of glycine and glyphosate and 1H, 13C, 31P, and 15N NMR spectroscopy we were able to identify all significant terminal chlorination products of glycine and glyphosate, and show that glyphosate degradation closely parallels that of glycine. We have determined that the C1 carboxylic acid carbon of glycine/glyphosate is quantitatively converted to CO2 upon chlorination. The C2 methylene carbon of glycine/glyphosate is converted to CO2 and methanediol. The relative abundance of these two products is a function of the pH of the chlorination reactions. Under near neutral to basic reaction conditions (pH 6-9), CO2 is the predominant product, whereas, under acidic reaction conditions (pH < 6) the formation of methanediol is favored. The C3 phosphonomethylene carbon of glyphosate is quantitatively converted to methanediol under all conditions tested. The nitrogen atom of glycine/glyphosate is transformed into nitrogen gas and nitrate, and the phosphorus moiety of glyphosate produces phosphoric acid upon chlorination. In addition to these terminal chlorination products, a number of labile intermediates were also identified including N-chloromethanimine, N-chloroaminomethanol, and cyanogen chloride. The chlorination products identified in this study are not unique to glyphosate and are similar to those expected from chlorination of amino acids, proteins, peptides, and many other natural organic matters present in drinking water.
Asunto(s)
Cloro/química , Glicina/análogos & derivados , Glicina/química , Purificación del Agua , Agua , Dióxido de Carbono/metabolismo , Isótopos de Carbono , Radioisótopos de Carbono , Cloro/metabolismo , Glicina/metabolismo , Espectroscopía de Resonancia Magnética , Metano/metabolismo , Isótopos de Nitrógeno , Purificación del Agua/métodos , GlifosatoRESUMEN
Glyphosate is the active ingredient in Roundup agricultural herbicides and other herbicide formulations that are widely used for agricultural, forestry, and residential weed control. As part of the Farm Family Exposure Study, we evaluated urinary glyphosate concentrations for 48 farmers, their spouses, and their 79 children (4-18 years of age). We evaluated 24-hr composite urine samples for each family member the day before, the day of, and for 3 days after a glyphosate application. Sixty percent of farmers had detectable levels of glyphosate in their urine on the day of application. The geometric mean (GM) concentration was 3 ppb, the maximum value was 233 ppb, and the highest estimated systemic dose was 0.004 mg/kg. Farmers who did not use rubber gloves had higher GM urinary concentrations than did other farmers (10 ppb vs. 2.0 ppb). For spouses, 4% had detectable levels in their urine on the day of application. Their maximum value was 3 ppb. For children, 12% had detectable glyphosate in their urine on the day of application, with a maximum concentration of 29 ppb. All but one of the children with detectable concentrations had helped with the application or were present during herbicide mixing, loading, or application. None of the systemic doses estimated in this study approached the U.S. Environmental Protection Agency reference dose for glyphosate of 2 mg/kg/day. Nonetheless, it is advisable to minimize exposure to pesticides, and this study did identify specific practices that could be modified to reduce the potential for exposure.