RESUMEN
The aim of this study is to evaluate the removal efficiency of iopromide using electron beam (E-beam) irradiation technology, and its degradation characteristics with hydroxyl radical (OH) and hydrated electron (e(aq)(-)). Studies are conducted with different initial concentrations of iopromide in pure water and in the presence of hydrogen peroxide, bicarbonate ion, or sulfite ion. E-beam absorbed dose of 19.6 kGy was required to achieve 90% degradation of 100 µM iopromide and the E-beam/H(2)O(2) system increased the removal efficiency by an amount of OH· generation. In the presence of OH scavengers (10 mM sulfite ion), the required dose for 90% removal of 100 µM iopromide was only 0.9 kGy. This greatly enhanced removal was achieved in the presence of OH· scavengers, which was rather unexpected and unlike the results obtained from most advanced oxidation process (AOP) experiments. The reasons for this enhancement can be explained by a kinetic study using the bimolecular rate constants of each reaction species. To explore the reaction scheme of iopromide with OH· or e(aq)(-) and the percent of mineralization for the two reaction paths, the total organic carbon (TOC), released iodide, and intermediates were analyzed.
Asunto(s)
Medios de Contraste/efectos de la radiación , Electrones , Yohexol/análogos & derivados , Contaminantes Químicos del Agua/efectos de la radiación , Purificación del Agua/métodos , Bicarbonatos/química , Medios de Contraste/química , Peróxido de Hidrógeno/química , Radical Hidroxilo/química , Yodo/química , Yohexol/química , Yohexol/efectos de la radiación , Sulfitos/química , Contaminantes Químicos del Agua/químicaRESUMEN
The aqueous degradation of iopromide, an iodinated X-ray contrast media (ICM) compound, by the combination of UV(254) irradiation and potassium peroxydisulfate (K(2)S(2)O(8)) has been studied in laboratory scale experiments. The influence of various parameters on the performance of the treatment process has been considered, namely the UV irradiation light intensity, the initial concentrations of iopromide and peroxydisulfate, and the initial solution pH. Iopromide degradation increased with UV light intensity and peroxydisulfate concentration, but decreased with initial pH. Under specific conditions complete removal of iopromide was achieved within 30 min, and near-complete mineralisation (loss of solution TOC) within 80 min. Degradation was believed to be caused by a combination of direct photolysis, sulphate radical attack, and, to a minor degree, direct oxidation by peroxydisulfate. Approximate values for the reaction rate constants have been determined and found to be equal to 1-2x10(4) M(-1) s(-1) for sulfate radicals, and 1-2 M(-2) s(-1) for S(2)O(8)(2-). Overall compound degradation was observed to follow first-order kinetics where the rate constant decreased with initial solution pH. During the reaction, the solution pH decreased as a consequence of sulfate radical scavenging.
Asunto(s)
Yohexol/análogos & derivados , Eliminación de Residuos Sanitarios/métodos , Peróxidos/química , Sulfatos/química , Rayos Ultravioleta , Medios de Contraste , Depuradores de Radicales Libres , Concentración de Iones de Hidrógeno , Yohexol/química , Yohexol/efectos de la radiación , Cinética , Oxidantes/químicaRESUMEN
The highly polar, nonionic X-ray contrast agent iopromide (C(18)H(24)N(3)O(8)I(3); 791 Da) is resistant to microbial degradation during the activated sludge process in wastewater treatment plants and hence is released into the aquatic environment. Against this background, the present study was conducted to evaluate the phototransformation, potentially constituting the most relevant removal mechanism in rivers and streams. The photolysis of the iodinated aromatic compound was investigated in a Suntest solar simulator using aqueous solutions. Following a 120-min irradiation period, an almost complete primary degradation of iopromide gave rise to a series of photoproducts that were chromatographed on a reversed-phase UPLC and subsequently characterized by a combination of accurate mass measurements on a ESI-QqToF-MS instrument and H/D-exchange experiments. This analytical approach facilitated confident identification of eight prominent products with the following elemental compositions and molecular weights: C(18)H(25)N(3)O(9)I(2) (681 Da); C(18)H(25)N(3)O(8)I(2) (665 Da); C(17)H(23)N(3)O(8)I(2) (651 Da); C(18)H(24)N(3)O(9)I (553 Da); C(17)H(24)N(3)O(8)I (525 Da); C(15)H(20)N(3)O(6)I (465 Da); C(14)H(18)N(3)O(6)I (451 Da); and C(18)H(25)N(3)O(9) (427 Da). Their formation was the result of four principal photoreactions: (1) gradual, and eventually complete, deiodination of the aromatic ring; (2) substitution of the halogen by a hydroxyl group; (3) N-dealkylation of the amide in the hydroxylated side chain; and (4) oxidation of a methylene group in the hydroxylated side chain to the corresponding ketone. In conclusion, the findings of the artificial sunlight irradiation experiments indicated that in real environmental settings iopromide might suffer partial or even complete deiodination.
Asunto(s)
Medios de Contraste/efectos de la radiación , Yohexol/análogos & derivados , Procesos Fotoquímicos , Cromatografía Líquida de Alta Presión , Medios de Contraste/química , Remoción de Radical Alquila , Medición de Intercambio de Deuterio , Residuos Industriales/análisis , Yohexol/química , Yohexol/efectos de la radiación , Estructura Molecular , Oxidación-Reducción , Fotólisis , Espectrometría de Masa por Ionización de Electrospray , Luz Solar , Espectrometría de Masas en Tándem , Contaminantes Químicos del Agua/químicaRESUMEN
The kinetics of Ultraviolet C (UV-C)-induced direct phototransformation of four representative pharmaceuticals, i.e., 17alpha-ethinylestradiol (EE2), diclofenac, sulfamethoxazole, and iopromide, was investigated in dilute solutions of pure water buffered at various pH values using a low-pressure and a medium-pressure mercury arc lamp. Except for iopromide, pH-dependent rate constants were observed, which could be related to acid-base equilibria. Quantum yields for direct phototransformation were found to be largely wavelength-independent, except for EE2. This compound, which also had a rather inefficient direct phototransformation, mainly underwent indirect phototransformation in natural water samples, while the UV-induced depletion of the other pharmaceuticals appeared to be unaffected by the presence of natural water components. At the UV-C (254 nm) drinking-water disinfection fluence (dose) of 400 Jm(-2), the degree of depletion of the select pharmaceuticals at pH=7.0 in pure water was 0.4% for EE2, 27% for diclofenac, 15% for sulfamethoxazole, and 15% for iopromide, indicating that phototransformation should be seriously taken into account when evaluating the possibility of formation of UV transformation products from pharmaceuticals present as micropollutants.
Asunto(s)
Diclofenaco/efectos de la radiación , Etinilestradiol/efectos de la radiación , Yohexol/análogos & derivados , Sulfametoxazol/efectos de la radiación , Contaminantes Químicos del Agua/efectos de la radiación , Yohexol/efectos de la radiación , Rayos Ultravioleta , Purificación del Agua/métodosRESUMEN
We hypothesize that iodine allergy is an immune response to iodinated autologous proteins generated in vivo from iodine-containing organic and inorganic chemicals. In this report, effects of protein iodination on elicitogenic activity in guinea pig iodine allergy model and iodinated protein antigen generation in vitro from iodine-containing chemicals were investigated. Active cutaneous anaphylaxis (ACA) and delayed-type hypersensitivity (DTH) tests were performed in guinea pigs immunized with iodine. The amount of iodine (I2) reacted to proteins for giving them an eliciting activity of ACA was > or = 0.15 micromol for 1 mg of albumin. DTH reactions were provoked by intradermal injection of 10(6) PECs reacted with > or = 0.075 micromol of I2. I2 was generated from a potassium iodide (KI) solution or iodinated contrast media by UV light irradiation. X-ray irradiation of KI and iodinated contrast media in the presence of protein resulted in the generation of iodinated protein antigens. The generation of iodinated protein antigens was inhibited in the presence of reducing agents. Therefore, it is noteworthy that iodine allergy of the present hypothesis is dependent on reactive oxygens. By presenting these ex vivo and in vitro data, we discuss the possibilities for the generation of iodinated protein antigens in vivo.
Asunto(s)
Medios de Contraste , Hipersensibilidad a las Drogas/etiología , Inmunización , Yodoproteínas/inmunología , Yoduro de Potasio , Traslado Adoptivo , Albúminas/química , Animales , Antígenos/inmunología , Antioxidantes/farmacología , Líquido Ascítico/citología , Líquido Ascítico/inmunología , Líquido Ascítico/metabolismo , Medios de Contraste/efectos adversos , Medios de Contraste/química , Medios de Contraste/efectos de la radiación , Modelos Animales de Enfermedad , Relación Dosis-Respuesta en la Radiación , Ensayo de Inmunoadsorción Enzimática , Femenino , Cobayas , Hipersensibilidad Tardía/inmunología , Yodoproteínas/síntesis química , Yodoproteínas/farmacología , Yohexol/efectos adversos , Yohexol/química , Yohexol/efectos de la radiación , Ácido Yotalámico/efectos adversos , Ácido Yotalámico/química , Ácido Yotalámico/efectos de la radiación , Anafilaxis Cutánea Pasiva/efectos de los fármacos , Anafilaxis Cutánea Pasiva/inmunología , Yoduro de Potasio/efectos adversos , Yoduro de Potasio/inmunología , Yoduro de Potasio/efectos de la radiación , Rayos Ultravioleta , Rayos XRESUMEN
PURPOSE: In XeCl-Excimer laser angioplasty, unintended and possibly harmful interaction of the UV-laser light and the contrast media may occur due to the high concentration of contrast medium proximal to the occlusion or subtotal stenosis. METHODS: One ml of three nonionic monomeric contrast agents (iopromide, iomeprol, iopamidol), one nonionic dimeric (jotrolane), and one ionic monomeric (amidotrizoate) X-ray contrast agent were irradiated with a XeCl excimer laser (lambda = 308 nm, pulse duration 120 ns, 50 Hz) using a 9 French multifiber catheter (12 sectors). Up to 20,000 pulses (106 J) were applied. Using high performance liquid chromatography the amount of liberated iodide as well as the fraction of unchanged contrast media were measured. Cytotoxicity of the photoproducts was tested in a colony formation assay of human skin fibroblasts. The contrast agents were irradiated with 2000 pulses/ml (5.3 mJ/pulse; 10.6 J) and then added to the cell cultures for a period of three hours in a concentration of 10%. RESULTS: Excimer laser irradiation induced iodide liberation of up to 3.3 mg iodide/ml. Up to 19% of the contrast agents changed their original molecular structure. Incubation of irradiated contrast agents resulted in a significantly decreased potential for colony formation (p values ranging from 0.0044 to 0.0102) with significantly higher toxicity of amidotrizoate and iomeprol in comparison to iopromide, iotrolan, and iopamidol. DISCUSSION: Due to the cytotoxic photoproducts and the high level of liberated iodide, it is recommended to flush the artery with physiological saline solution before applying a pulsed excimer laser in human arterial obstructions in order to reduce the contrast agent concentration at the site of irradiation.