Análisis de residuos de herbicidas en aguas procedentes de Navarra mediante lc-ms/ms / Lc-ms/ms analysis of herbicide residues in waters from Navarre

Fundamento. El objetivo del trabajo fue obtener informaciónacerca de los residuos de herbicidas (imazametabenz,simazina, isoproturon, clortoluron, metribuzina,atrazina, cianazina, terbutrina, propanil,terbutilazina, alacloro y pendimetalina) presentes enaguas procedentes de Navarra.Material y métodos. Se tomó un total de 465 muestrasde agua; de ellas, 378 se obtuvieron en 141 abastecimientos;las 87 restantes procedieron de 37 fuentes,manantiales y sondeos situados en zonas agrícolas delsur de Navarra. La técnica empleada fue LC-MS/MS.Resultados. Se detectaron residuos de herbicidas en el33% de los abastecimientos, y su concentración superóel límite normativo en el 8% de ellos. Se encontraron residuosde herbicidas en el 86% de las muestras de pozos yfuentes de zonas agrícolas del sur de Navarra. El númerode abastecimientos con residuos de herbicidas aumentóde norte a sur de Navarra. No obstante, el porcentaje deabastecimientos en los que la concentración de herbicidassuperó los límites fue mayor en la zona centro de Navarraque en la zona sur y norte. Imazametabenz fue el herbicidamás detectado en las muestras de las zonas norte, centro ysur. Atrazina, terbutilazina e imazametabenz se detectaronpreferentemente en las muestras de la zona sur.Conclusiones. Las diferencias entre las tres zonas deNavarra pueden explicarse atendiendo a las diferentesprácticas agrícolas de cada región. No se detectaronconcentraciones de herbicidas superiores a los límitesnormativos en ninguna de las muestras de agua procedentesde las poblaciones mayoritarias de Navarra(AU)

Background. The aim of the study was to obtain informationon the residues of herbicides (imazametabenz,simazine, isoproturon, clortoluron, metribuzine, atrazine,cianazine, terbutrin, propanil, terbutilazine, alachlorand pendimetalin) present in water proceedingfrom Navarre.Material and methods. A total of 465 samples of waterwere taken: 378 were taken from 141 water supplies; theremaining 87 proceeded from fountains, springs and boringsin agricultural areas in the south of Navarre. Thetechnique employed was LC-MS/MS.Results. Herbicide residues were detected in 33% of thewater supplies, and their concentration exceeded thenormative limit in 8% of them. Herbicide residues werefound in 86% of the samples from wells and fountains ofthe agricultural areas of the south of Navarre. The numberof water supplies with herbicide residues increased fromnorth to south. However, the percentage of water suppliesin which the concentration of herbicides exceeded the limitswas greater in the centre of Navarre than in the northand south. Imazametabenz was the herbicide most detectedin the samples from the northern, central and southernareas. Atrazine, terbutilazine and imazametabenz weremost detected in the samples of the southern area.Conclusions. The differences amongst the three areasof Navarre can be explained as being due to the differentagricultural practices of each area. Concentrationsof herbicides exceeding the normative limits were notdetected in any of the water samples proceeding fromthe larger towns of Navarre(AU)

[LC-MS/MS analysis of herbicide residues in waters from Navarre]. / Análisis de residuos de herbicidas en aguas procedentes de Navarra mediante LC-MS/MS.

BACKGROUND: The aim of the study was to obtain information on the residues of herbicides (imazametabenz, simazine, isoproturon, clortoluron, metribuzine, atrazine, cianazine, terbutrin, propanil, terbutilazine, alachlor and pendimetalin) present in water proceeding from Navarre. MATERIAL AND METHODS: A total of 465 samples of water were taken: 378 were taken from 141 water supplies; the remaining 87 proceeded from fountains, springs and borings in agricultural areas in the south of Navarre. The technique employed was LC-MS/MS. RESULTS: Herbicide residues were detected in 33% of the water supplies, and their concentration exceeded the normative limit in 8% of them. Herbicide residues were found in 86% of the samples from wells and fountains of the agricultural areas of the south of Navarre. The number of water supplies with herbicide residues increased from north to south. However, the percentage of water supplies in which the concentration of herbicides exceeded the limits was greater in the centre of Navarre than in the north and south. Imazametabenz was the herbicide most detected in the samples from the northern, central and southern areas. Atrazine, terbutilazine and imazametabenz were most detected in the samples of the southern area. CONCLUSIONS: The differences amongst the three areas of Navarre can be explained as being due to the different agricultural practices of each area. Concentrations of herbicides exceeding the normative limits were not detected in any of the water samples proceeding from the larger towns of Navarre.

[Organic pollutant residues of different origins in Navarra]. / Residuos de contaminantes orgánicos de diferentes orígenes en Navarra.

An analysis was made of residues of polychlorobyphenyls and trihalomethanes through GC-ECD and of herbicides through HPLC-PAD in samples proceeding from Navarra. Polychlorobyphenyls were detected (0.30 +/- 0.05 and 0.11 +/- 0.05 microg/l) in two of the 106 water samples analysed. Sixty-six food samples were analysed, and polychlorobyphenyls were only found in 8 samples of trout (dissimilar to dioxins: 21-194 microg/kg of fat; similar to dioxins: 41-139 microg/kg of fat). Of 107 fat samples analysed, polychlorobyphenyls dissimilar to dioxins were detected in two (27 +/- 5 and 30 +/- 5 microg/kg). Out of a total of 94 feed samples analysed, polychlorobyphenyls were detected in all the samples (12) of feed for aquaculture and their raw materials; the concentration of polychlorobyphenyls dissimilar to dioxins varied by an interval of 8-247 microg/kg of fat; polychlorobyphenyls similar to dioxins, between 18 and 107 microg/kg of fat. Contamination by polychlorobyphenyls of the fish from aquaculture could be due to the feed used in these exploitations. The average of trihalomethanes in the waters of the southern zone of Navarra (44 +/- 4 microg/l) was higher than those of the middle zone (16 +/- 1 microg/l) and the mountain zone (12 +/- 1 microg/l). The concentration of 99% of the samples fulfilled the norms on halomethanes. A relation was observed between muddiness and the concentration of trihalomethanes. Herbicide (cianazine) was only detected in one of the 135 samples of water analysed, with a concentration of (0.4 +/- 0.2 microg/l) which exceeded the established limit. The use of confirmation techniques (GC-MS, HPLC-MS/MS) would make it possible to validate these results and to expand the number of compounds analysed.

Residuos de contaminantes orgánicos de diferentes orígenes en Navarra / Organic pollutant residues of different origins in Navarra

Se analizaron residuos de policlorobifenilos, de trihalometanos mediante GC-ECD y de herbicidas mediante HPLC-PAD en muestras procedentes de Navarra.Se detectó policlorobifenilos (0,30 ± 0,05 y 0,11 ± 0,05 µg/l) en dos de las 106 aguas analizadas. Se analizó 66 muestras de alimentos, y sólo se halló policlorobifenilos en 8 muestras de trucha (no similares a dioxinas: 21-194 µg/kg de grasa; similares a dioxinas: 41-139 µg/kg de grasa). De 107 grasas analizadas, se encontró policlorobifenilos no similares a dioxinas en dos de ellas (27 ± 5 y 30 ± 5 µg/kg). De un total de 94 piensos, se detectó policlorobifenilos en todas las muestras (12) de pienso para acuicultura y sus materias primas; la concentración de policlorobifenilos no similares a dioxinas varió en el intervalo 8-247 µg/kg de grasa; la de los similares a dioxinas, entre 18 y 107 µg/kg de grasa. La contaminación por policlorobifenilos del pescado de acuicultura pudo deberse a los piensos utilizados en estas explotaciones.La concentración media de trihalometanos en las aguas de la Ribera de Navarra (44 ± 4 µg/l) fue superior a la de la zona media (16 ± 1 µg/l) y a la de la montaña (12 ± 1 µg/l). La concentración del 99% de las muestras cumple la normativa sobre halometanos. Se observó una relación entre la turbidez y la concentración de trihalometanos.Sólo se detectó un herbicida (cianazina) en una de las 135 muestras de agua analizadas, con una concentración (0,4 ± 0,2 µg/l) que superaba el límite establecido.La utilización de técnicas confirmatorias (GC-MS, HPLC-MS/MS) permitiría convalidar estos resultados, y ampliar el número de compuestos analizados

An analysis was made of residues of polychlorobyphenyls and trihalomethanes through GC-ECD and of herbicides through HPLC-PAD in samples proceeding from Navarra. Polychlorobyphenyls were detected (0.30 ± 0.05 and 0.11 ± 0.05 µg/l) in two of the 106 water samples analysed. Sixty-six food samples were analysed, and polychlorobyphenyls were only found in 8 samples of trout (dissimilar to dioxins: 21-194 µg/kg of fat; similar to dioxins: 41-139 µg/kg of fat). Of 107 fat samples analysed, polychlorobyphenyls dissimilar to dioxins were detected in two (27 ± 5 and 30 ± 5 µg/kg). Out of a total of 94 feed samples analysed, polychlorobyphenyls were detected in all the samples (12) of feed for aquaculture and their raw materials; the concentration of polychlorobyphenyls dissimilar to dioxins varied by an interval of 8-247 µg/kg of fat; polychlorobyphenyls similar to dioxins, between 18 and 107 µg/kg of fat. Contamination by polychlorobyphenyls of the fish from aquaculture could be due to the feed used in these exploitations. The average of trihalomethanes in the waters of the southern zone of Navarra (44 ± 4 µg/l) was higher than those of the middle zone (16 ± 1 µg/l) and the mountain zone (12 ± 1 µg/l). The concentration of 99% of the samples fulfilled the norms on halomethanes. A relation was observed between muddiness and the concentration of trihalomethanes. Herbicide (cianazine) was only detected in one of the 135 samples of water analysed, with a concentration of (0.4 ± 0.2 µg/l) which exceeded the established limit. The use of confirmation techniques (GC-MS, HPLC-MS/MS) would make it possible to validate these results and to expand the number of compounds analysed

[A case of recurrent mediastinal goiter (oxyphilic cell carcinoma)].

A case of recurrent mediastinal goiter (oxyphilic cell carcinoma) in a 66-year-old female was reported. 19 years ago, the patient submitted to a right-hemithyroidectomy for the oxyphilic cell adenoma. Since two months, her dyspnea gradually aggravated. On admission, abnormal mass of right upper mediastinum was shown by chest X-ray. CT scan and MRI showed a 8 cm sized right upper mediastinal tumor with tracheal compression.

[Investigation of hepatic energy metabolism in normothermic hepatic ischemia--comparison between normal and cirrhotic rat liver].

The purpose of this study was to investigate the energy movement of the normothermic ischemic liver. Liver ischemia was induced in normal and cirrhotic rats, by cross-clamping portal vein and hepatic artery, bypassing the portal blood to the jugular vein through a shunt tube. The levels of ATP of the hepatic tissue was measured before and after hepatic ischemia, by HPLC and 31P-NMR. Before hepatic ischemia, the levels of ATP was greater in normal liver than in cirrhotic liver, but after ischemia it was significantly smaller in normal liver than cirrhotic liver. Generally they say that the greater is the ATP of the tissue, the greater is the viability of the tissue. But this experiment showed the contrary. Cirrhotic liver can't use glucose sufficiently, therefore acetyl-CoA, which is used in TCA-cycle, is derived from the resolution of fatty acid. As a result, free fatty acid and acyl-CoA increase in cirrhotic liver, and suppress Na(+)-K(+)-ATPase. I conclude that the cirrhotic liver can't effectively use ATP to maintain the potential of the liver cells, maybe, because of it's abnormal metabolism of glucose. Therefore, the levels of ATP was greater in cirrhotic liver than in normal liver after hepatic ischemia.

Surgical experience with nonparasitic cysts of the liver--the characteristics and constituents of cyst fluid.

Fifteen patients with nonparasitic hepatic cysts underwent surgery to relieve abdominal complaints, at the First Surgical Department, Tokyo University Hospital between 1966 and 1989. Total removal of the cyst was carried out in 14 of the patients, while puncture and aspiration only were performed in the other patient in whom a cyst had ruptured spontaneously, after which hemoperitoneum was observed at emergency laparotomy. The size of the cysts varied from 7-19 cm with a mean of 12.4 cm. Histological study revealed a congenital cyst in 14 patients and a cystadenoma in one. The epithelium lining of the internal surface of the congenital cysts was highly atrophic and desolated and often disappeared. Examination of the cyst fluid revealed the same concentration of electrolytes as in the serum. Hepatic enzyme levels were usually lower than in the serum, but lactic dehydrogenase and aminotransferase levels were elevated in a few cases. Tumor marker levels of the cyst fluid were higher than those in the serum in four of five patients examined.

[Liver tissue pH measurement can predict survival in rats undergoing normothermic ischemias].

The purpose of this study was to evaluate the usefulness of pH measurement of the liver for the prediction of survival after normothermic hepatic ischemia. Liver ischemia was induced in rats with cirrhosis and normal liver by cross-clamping of the portal vein and hepatic artery, bypassing the portal blood to the jugular vein through a shunt tube. The ischemic time periods were selected arbitrarily from 15 to 95 minutes. Preischemic liver function test was assessed by indocyanine green dye. I measured liver tissue pH continuously during the ischemic period. In addition, levels of adenosine triphosphate (ATP) of the hepatic tissue was determined every ten minutes after ischemia by HPLC and energy charge was calculated. There was a significant positive correlation between the postischemic change of the liver tissue pH and that of energy charge. A discriminant analysis yielded an equation predictive of survival: Y = 7.2 *delta pH10 + 27.15 *KICG - 0.07 *ischemic time - (Y greater than or equal to 0; survivors, Y less than 0; nonsurvivors, delta pH10; preischemic pH - pH at 10 minutes after ischemia). The equation predicted survival with 77.8% accuracy. I conclude that liver tissue pH reflects energy charge of the liver during the ischemic period and pH measurement can predict survival with high accuracy in rats undergoing normothermic ischemia.