996 resultados para d18O H2O


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J. Am. Chem. Soc., 2003, 125 (51), pp 15708–15709 DOI: 10.1021/ja038344n

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Dissertation for the Master Degree in Technology and Food Security

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New emerging contaminants could represent a danger to the environment and Humanity with repercussions not yet known. One of the major worldwide pharmaceutical and personal care productions are antimicrobials products, triclosan, is an antimicrobial agent present in most products. Despite the high removal rate of triclosan present in wastewater treatments, triclosan levels are on the rise in the environment through disposal of wastewater effluent and use of sewage sludge in land application. Regulated in the EC/1272/2008 (annex VI, table 3.1), this compound is considered very toxic to aquatic life and it has been reported that photochemical transformation of triclosan produces dioxins. In the current work it was defined three objectives; determination of the most efficient process in triclosan degradation, recurring to photochemical degradation methods comparing different sources of light; identification of the main by-products formed during the degradation and the study of the influence of the Fenton and photo-Fenton reaction. Photochemical degradation methods such as: photocatalysis under florescent light (UV), photocatalysis under visible light (sunlight), photocatalysis under LEDs, photo-Fenton and Fenton reaction have been compared in this work. The degradation of triclosan was visualized through gas chromatography/mass spectrometry (GC/MS). In this study photo-Fenton reaction has successfully oxidized triclosan to H2O and CO2 without any by-products within 2 hours. Photocatalysis by titanium dioxide (TiO2) under LEDs was possible, having a degradation rate of 53% in an 8 hours essay. The degradation rate of the Fenton reaction, UV light and sunlight showed degradation between 90% and 95%. The results are reported to the data observed without statistic support, since this was not possible during the work period. Hydroquinone specie and 2,4-dichlorophenol by-products were identified in the first hour of photocatalysis by UV. A common compound, possibly identified has C7O4H , was present at the degradation by UV, sunlight and LEDs and was concluded to be a contaminant. In the future more studies in the use of LEDs should be undertaken given the advantages of long durability and low consumption of energy of these lamps and that due to their negative impact on the environment fluorescent lamps are being progressively made unavailable by governments, requiring new solutions to be found. Fenton and photo-Fenton reactions can also be costly processes given the expensive reagents used.

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OBJECTIVE: To evaluate the effects of 2 different doses of exogenous surfactant on pulmonary mechanics and on the regularity of pulmonary parenchyma inflation in newborn rabbits. METHOD: Newborn rabbits were submitted to tracheostomy and randomized into 4 study groups: the Control group did not receive any material inside the trachea; the MEC group was instilled with meconium, without surfactant treatment; the S100 and S200 groups were instilled with meconium and were treated with 100 and 200 mg/kg of exogenous surfactant (produced by Instituto Butantan) respectively. Animals from the 4 groups were mechanically ventilated during a 25-minute period. Dynamic compliance, ventilatory pressure, tidal volume, and maximum lung volume (P-V curve) were evaluated. Histological analysis was conducted using the mean linear intercept (Lm), and the lung tissue distortion index (SDI) was derived from the standard deviation of the means of the Lm. One-way analysis of variance was used with a = 0.05. RESULTS: After 25 minutes of ventilation, dynamic compliance (mL/cm H2O · kg) was 0.87 ± 0.07 (Control); 0.49 ± 0.04 (MEC*); 0.67 ± 0.06 (S100); and 0.67 ± 0.08 (S200), and ventilatory pressure (cm H2O) was 9.0 ± 0.9 (Control); 16.5 ± 1.7 (MEC*); 12.4 ± 1.1 (S100); and 12.1 ± 1.5 (S200). Both treated groups had lower Lm values and more homogeneity in the lung parenchyma compared to the MEC group: SDI = 7.5 ± 1.9 (Control); 11.3 ± 2.5 (MEC*), 5.8 ± 1.9 (S100); and 6.7 ± 1.7 (S200) (*P < 0.05 versus all the other groups). CONCLUSIONS: Animals treated with surfactant showed significant improvement in pulmonary mechanics and more regularity of the lung parenchyma in comparison to untreated animals. There was no difference in results after treatment with either of the doses used.

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In the Brazilian Amazon, large areas of abandoned lands may revert to secondary forest. In the process, pioneer tree species have an important role to restore productivity in old fields and improve environmental conditions. To determine potential photosynthesis (Apot), stomatal conductance (g), transpiration (E), and leaf micronutrient concentrations in Ochroma pyramidale (Cav. ex Lam.) Urban a study was carried out in the Brazilian Amazon (01o 51' S; 60o 04' W). Photosynthetic parameters were measured at increasing [CO2], saturating light intensity (1 mmol (photons) m-2 s-1), and ambient temperature. The rate of electron-transport (J), Apot,and water-use efficiency (WUE) increased consistently at increasing internal CO2 concentration (Ci). Conversely, increasing [CO2] decreased gs, E, and photorespiration (Pr). At the CO2-saturated region of the CO2 response curve (1.1 mmol (CO2) mol-1(air), J was 120 μmol (e-) m-2s-1 and Apot reached up to 24 μmol (CO2) m-2s-1. Likewise, at saturating C1 g and E were 30 and 1.4 mmol (H2O) m-2s-1, respectively, and P 2 r about 1.5 μmol (CO2) m-2s-1. Foliar nutrients were 185, 134, 50, and 10 μmol (element) m-2 (leaf area) for Fe, Mn, Zn, and Cu, respectively. It was concluded that [CO ] probably limits light saturated photosynthesis in this site. Furthermore, from a nutritional point of view, the low Fe to Cu ratio (15:1) may reflect nutritional imbalance in O. pyramidale at this site.

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As rochas basálticas possuem composição rica em elementos químicos considerados nutrientes às plantas, o que a torna apta para o uso agrícola, melhorando a fertilidade dos solos. Objetivou-se com esse trabalho avaliar o efeito de doses de basalto moído nos teores de alguns nutrientes no solo. Foi utilizado um Latossolo Amarelo ácido e de baixa CTC, formação geológica Boa Vista, estado de Roraima. A rocha basáltica da formação Apoteri foi coletada na pedreira da serra de Nova Olinda, Boa Vista. Os tratamentos consistiram da incorporação e incubação de oito doses do pó da rocha (0; 0,85; 1,70; 3,35; 5,03; 10,05; 20,40 e 40,80 g kg-1, correspondente a 0; 2,0; 4,0; 8,0; 12,0; 24,0; 48,0 e 96 t ha-1). O delineamento experimental foi inteiramente casualizado com oito tratamentos e três repetições. Após a incorporação do basalto moído ao solo e por um período 180 dias de incubação, o solo foi analisado quanto aos teores de Ca2+, Mg2+ e Al3+ trocáveis, acidez potencial (H+Al), teores disponíveis de Zn, Fe, Cu e Mn e valores de pH em H2O e em KCl. A dose de 20,40 g kg-1 de basalto proporcionou a máxima redução da acidez ativa, com pH aumentando de 4,8 para 5,5. Os teores de Ca2+ e Mg2+ trocáveis aumentaram, porém proporcionaram baixos incrementos desses cátions no solo. As doses de basalto apresentaram alta eficiência para a neutralização da acidez potencial. A adição do basalto moído proporcionou incremento nos teores de Zn, Fe e Cu no solo com o tempo de incubação.

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The presence of mycotoxins in foodstuff is a matter of concern for food safety. Mycotoxins are toxic secondary metabolites produced by certain molds, being ochratoxin A (OTA) one of the most relevant. Wines can also be contaminated with these toxicants. Several authors have demonstrated the presence of mycotoxins in wine, especially ochratoxin A (OTA) [1]. Its chemical structure is a dihydro-isocoumarin connected at the 7-carboxy group to a molecule of L--phenylalanine via an amide bond. As these toxicants can never be completely removed from the food chain, many countries have defined levels in food in order to attend health concerns. OTA contamination of wines might be a risk to consumer health, thus requiring treatments to achieve acceptable standards for human consumption [2]. The maximum acceptable level of OTA in wines is 2.0 g/kg according to the Commission regulation No. 1881/2006 [3]. Therefore, the aim of this work was to reduce OTA to safer levels using different fining agents, as well as their impact on white wine physicochemical characteristics. To evaluate their efficiency, 11 commercial fining agents (mineral, synthetic, animal and vegetable proteins) were used to get new approaches on OTA removal from white wine. Trials (including a control without addition of a fining agent) were performed in white wine artificially supplemented with OTA (10 µg/L). OTA analysis were performed after wine fining. Wine was centrifuged at 4000 rpm for 10 min and 1 mL of the supernatant was collected and added of an equal volume of acetonitrile/methanol/acetic acid (78:20:2 v/v/v). Also, the solid fractions obtained after fining, were centrifuged (4000 rpm, 15 min), the resulting supernatant discarded, and the pellet extracted with 1 mL of the above solution and 1 mL of H2O. OTA analysis was performed by HPLC with fluorescence detection according to Abrunhosa and Venâncio [4]. The most effective fining agent in removing OTA (80%) from white wine was a commercial formulation that contains gelatine, bentonite and activated carbon. Removals between 10-30% were obtained with potassium caseinate, yeast cell walls and pea protein. With bentonites, carboxymethylcellulose, polyvinylpolypyrrolidone and chitosan no considerable OTA removal was verified. Following, the effectiveness of seven commercial activated carbons was also evaluated and compared with the commercial formulation that contains gelatine, bentonite and activated carbon. The different activated carbons were applied at the concentration recommended by the manufacturer in order to evaluate their efficiency in reducing OTA levels. Trial and OTA analysis were performed as explained previously. The results showed that in white wine all activated carbons except one reduced 100% of OTA. The commercial formulation that contains gelatine, bentonite and activated carbon (C8) reduced only 73% of OTA concentration. These results may provide useful information for winemakers, namely for the selection of the most appropriate oenological product for OTA removal, reducing wine toxicity and simultaneously enhancing food safety and wine quality.

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OBJECTIVE: To compare immediate and late results in patients with or without fenestration who underwent cavopulmonary anastomosis so that we could assess the efficiency of the technique. METHODS: Sixty-two patients underwent surgery between 1988 and 1999, 41 with fenestration (group I -G I) and 21 without fenestration (group II -G II). Tricuspid atresia was prevalent in group I (23-56%) and single ventricle was prevalent in group II (14-66%). Mean ages at the time of operation were 7.3 years in group I and 7.6 in group II. At late follow-up, mean ages were 10.6 years in group I and 12.8 years in group II. RESULTS: Immediate and late mortality were 7.3% in G-I and 4.7% in G-II. Significant pleural effusion occurred in 41.4% of G-I patients and in 23.8% of G-II patients. Significant pericardial effusion occurred in 29.2% and 14.2%, respectively, in groups I and II. Central venous pressure was greater in G-II, 17.7 cm in H2O, as opposed to 15 cm in G-I. Hospital stay was similar between the groups, 26.3 and 21.8 days, respectively. Cyanosis and arterial insaturation occurred in 5 patients, and 4 patients were in functional class II, all from G-I. At late follow-up, 58 (93.5%) were in functional class I. Sinus rhythm was present in 94%, and pulmonary perfusion was similar in both groups. Eleven patients who underwent spirometry had good tolerance to physical effort. CONCLUSION: Atrial fenestration did not improve the immediate or late follow-up of patients who underwent cavopulmonary anastomosis, and is, therefore, dispensable.

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El proyecto abarca diferentes aspectos relacionados con la electroquímica de moléculas orgánicas, priorizando las de interés biológico. Se estudia el comportamiento electroquímico de los sistemas enzimáticos, de los macrociclos y sus complejos de inclusión y de las interfases líquido/líquido modificadas o no por monocapas de sustancias anfipáticas, frente al transporte de iones, iones complejos e ionóforos. Se estudian además procesos de adsorción de iones complejos aplicables al análisis de trazas de iones metálicos. En todos los casos se estudian aspectos básicos y sus aplicaciones electroanalíticas. 1) Comportamiento electroquímico de moléculas orgánicas y de sus complejos de inclusión con ciclodextrinas: se estudia el efecto del macrociclo sobre la reacción de transferencia de carga del ácido ascórbico y de otras moléculas de estructura fenólica o derivados de los catecoles, tales como neurotransmisores y sus metabolitos relacionados. 2) Electrodos enzimáticos: se estudia el comportamiento de polifenol oxidasas provenientes de diversas fuentes, frente a sustratos fenólicos o derivados de catecoles, tales como neurotransmisores y sus metabolitos relacionados. Las enzimas se inmovilizan sobre electrodos de carbono y sobre electrodos de sales orgánicas conductoras mediante diferentes metodologías. Se analizan las aplicaciones analíticas. 3) Interfases líquidas: se continúa con el estudio de la transferencia de iones a través de la interfase H2O/1,2-dicloroetano modificada por la presencia de una monocapa de fosfolípido, como así también del mecanismo de transporte de cationes alcalinos y alcalino-térreos en presencia de distintos ligandos. 4) Estudio de la adsorción de complejos de cationes metálicos sobre electrodos de mercurio y de carbono. Se determinan parámetros de la etapa de transferencia de masa y de la adsorción propiamente dicha, tendientes a establecer los mecanismos de reacciones involucradas en las técnicas voltamétricas de adsorción-desorción. Se compara con técnicas voltamétricas de deposición disolución para los mismos cationes metálicos, con especial énfasis en las aplicaciones analíticas relacionadas con la determinación de cationes metálicos a nivel de trazas.

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Este trabalho relata os resultados de um ensaio realizado com o objetivo de estudar a fixação de P por um Latossolo Vermelho Escuro-Orto, serie Iracema, de Piracicaba, Estado de São Paulo. O ensaio foi realizado em vasos de plástico, cada um recebendo 500 g de terra e os tratamentos, correspondentes a 0, 100, 200, 400, 600 e 1.200 kg/ha de P2O5 na forma de Ca (H2PO4)2. H2O. Houve 4 repetições de cada tratamento. Seguiu-se um período de incubação de 3 semanas, durante o qual as parcelas permaneceram umidecidas, entre 40 e 70% do poder de retenção de umidade. Depois foram feitos trabalhos necessários do que se concluiu que: a) grande proporção do P fixado permaneceu solúvel em H2SO4 0,05 N; b) o Fe e o Al foram importantes na fixação do P; c) o pré-tratamento do solo com Ca (H2P0(4))2· H2O reduziu-lhe a capacidade de fixação de fosfato.

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Devido a numerosas discrepâncias nos resultados de estudos experimentais relativos à interação flúor-manganês, propusemo-nos a verificar se a adição de manganês 5 água fluoretada (1 ppm), em diferentes proporções fluor-manganês, levaria a uma diferente fixaçao do halogênio. Para tanto, 24 ratos Wistar, recém-desmamados, foram mantidos em dieta padrão de caseína a 27%, recebendo na sua água de consumo: 1) H2O destilada (controle); 2) 1,0 ppm de flúor: 3) 1,0 ppm de flúor + 0,5 ppm de manganês (F:Mn = 2,0); 4) 1,0 ppm de flúor +1,0 ppm de manganês (F: Mn = 1,0). Foram anotados o peso ganho e o consumo de alimento e água, durante os 60 dias de experimento, após o qual as patas traseiras, dos animais sacrificados, foram autoclavadas e desossadas, e os femures retirados. Posteriormente, foram estes submetidos à secagem, extração da gordura, pulverização e analise do flúor fixado. Também foram efetuadas analises da composição centesimal da ração e de flúor e manganês nesta e nas diferentes águas de consumo. Os resultados de percentagem do flúor ingerido fixado nos femures, foram analisados estatisticamente pelo teste não-paramétrico de Kruskal-Wallis (níveis de 1% e 5%) mostrando que, para as proporções consideradas, o flúor na taxa de 1 ppm, o manganês, quando administrado após o desmame, parece não afetar a fixaçao do flúor. Contudo, faz-se necessário dar continuidade aos estudos com novas proporções e taxas mais elevadas de flúor e manganês.

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Abstract : Textural division of a mineral in pyramids, with their apices located at the centre of the mineral and their bases corresponding to the mineral faces is called textural sector zoning. Textural sector zoning is observed in many metamorphic minerals like andalousite and garnet. Garnets found in the graphite rich black shales of the Mesozoic cover of the Gotthard Massif display textural sector zoning. The morphology of this sector zoning is not the same in different types of black shales observed in the Nufenen pass area. Garnets in foliated black shales display a well developed sector zoning while garnets found in cm-scale layered black shales display well developed sectors in the direction of the schistosity plane. This sector zoning is always associated with up to 30μm sized birefringent lamellae emanating radial from the sector boundaries. They alternate with isotrope lamellae. The garnet forming reaction was determined using singular value decomposition approach and results compared to thermodynamic calculations. It is of the form chl + mu + cc + cld = bt + fds + ank + gt + czo and is similar in both layered and foliated black shales. The calculated X(O) is close to 0.36 and does not significantly vary during the metamorphic history of the rock. This corresponds to X CO2, X CH4, and X H2O BSE imaging of garnets on oriented-cuts revealed that the orientation of the lamellae found within the sectors is controlled by crystallography. BSE imaging and electron microprobe analysis revealed that these lamellae are calcium rich compared to the isotropic lamellae. The addition of Ca to an almandine rich garnet causes a small distortion of the X site and potentially, ordering. Ordered and disordered garnet might have very similar free energies for this composition. Hence, two garnets with different composition can be precipitated with minor overstepping of the reaction. It is enough that continued nucleation of a new garnet layer slightly prefers the same structure to assure a fiber-like growth of both garnet compositions side by side. This hypothesis is in agreement with the thermodynamic properties of the garnet solid solution described in the literature and could explain the textures observed in garnets with these compositions. To understand the differences in sector zoning morphology, and crystal growth kinetics, crystal size distribution were determined in several samples using 2D spatial analysis of slab surfaces. The same nucleation rate law was chosen for all cases. Different growth rate law for non-layered black shales and layered black shales were used. Garnet in layered black shales grew according to a growth rate law of the form R=kt ½. The transport of nutrient is the limiting factor. Transport will occur preferentially on the schistosity planes. The shapes of the garnets in such rocks are therefore ovoid with the longest axis parallel to the schistosity planes. Sector zoning is less developed with sectors present only parallel to the schistosity planes. Garnet in non-layered blackshales grew according to a growth rate law of the form R=kt. The limiting factor is the attachment at the surface of the garnet. Garnets in these rocks will display a well developed sector zoning in all directions. The growth rate law is thus influenced by the texture of the rock. It favours or hinders the transport of nutrient to the mineral surface. Résumé : La zonation sectorielle texturale consiste en la division d'un cristal en pyramides dont les sommets sont localisés au centre du minéral. La base de ces pyramides correspond aux faces du minéral. Ce type de zonation est fréquemment observé dans les minéraux métamorphiques tels que l'andalousite ou le grenat. Les grenats présents dans les marnes riches en graphites de la couverture Mésozoïque du Massif du Gotthard présent une zonation sectorielle texturale. La morphologie de cette zonation n'est pas la même dans les marnes litées et dans les marnes foliées. Les grenats des marnes foliées montrent des secteurs bien développés dans 3 directions. Les grenats des marnes litées montrent des secteurs développés uniquement dans la direction des plans de schistosité. Cette zonation sectorielle est toujours associée à des lamelles biréfringentes de quelques microns de large qui partent de la limite des secteurs et qui sont perpendiculaires aux faces du grenat. Ces lamelles alternent avec des lamelles isotropes. La réaction de formation du grenat a été déterminée par calcul matriciel et thermodynamique. La réaction est de la forme chl + mu + cc + cld= bt + fds + ank + gt + czo. Elle est similaire dans les roches litées et dans les roches foliées. L'évaluation des conditions fluides montrent que le X(O) est proche de 0.36 et ne change pas de façon significative durant l'histoire métamorphique de la roche. Des images BSE sur des coupes orientées ont révélé que l'orientation de lamelles biréfringentes est contrôlée parla crystallographie. La comparaison des analyses à la microsonde électronique et des images BSE révèle également que les lamelles biréfringentes sont plus riches en calcium que les lamelles isotropes. L'addition de calcium va déformer légèrement le site X et ainsi créer un ordre sur ce site. L'énergie interne d'un grenat ordré et d'un grenat désordonné sont suffisamment proches pour qu'un léger dépassement de l'énergie de la réaction de formation permette la coexistence des 2 types de grenat dans le même minéral. La formation de lamelles est expliquée par le fait qu'un grenat préférera la même structure. Ces observations sont en accord avec la thermodynamique des solutions solides du grenat et permet d'expliquer les structures similaires observées dans des grenats provenant de lithologies différentes. Une étude de la distribution des tailles des grenats et une modélisation de la croissance a permis de mettre en évidence 2 mécanismes de croissance différents suivant la texture de la roche. Dans les 2 cas, la loi de nucléation est la même. Dans les roches litées, la loi de croissance est de forme R=kt½. Le transport des nutriments est le facteur limitant. Ce transport a lieu préférentiellement dans la direction des niveaux de schistosité. Les grenats ont une forme légèrement allongée car la croissance des secteurs est facilitée sur les niveaux de schistosité. La croissance des grenats dans les roches foliées suit une loi de croissance de la forme R=kt. Les seuls facteurs limitant la croissance sont les processus d'attachement à la surface du grenat. La loi de croissance de ces grenats est donc contrainte par la texture de la roche. Cela se marque par des différences dans la morphologie de la zonation sectorielle.

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Investigación realizada a partir de una estancia como profesor visitante en el Departamento de Ingeniería Mecánica de la Universitat Rovira i Virgili. Las soluciones acuosas de LiNO3 tienen una gran potencialidad para ser utilizadas como fluidos de trabajo en ciclos de absorción a altas temperaturas. La adición de otros nitratos y/o nitritos alcalinos mejora, entre otras propiedades, su solubilidad en H2O, el principal inconveniente de estas soluciones. La información bibliográfica sobre la solubilidad de estas es prácticamente inexistente, por eso, en este trabajo se ha realizado un estudio teórico-práctico de la solubilidad de algunos de estos sistemas.(...)

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BACKGROUND: Dissection during laparoscopic surgery produces smoke containing potentially toxic substances. The aim of the present study was to analyze smoke samples produced during laparoscopic colon surgery using a bipolar vessel sealing device (LigaSuretrade mark). METHODS: Four consecutive patients undergoing left-sided colectomy were enrolled in this pilot study. Smoke was produced by the use of LigaSuretrade mark. Samples (5,5l) were evacuated from the pneumoperitoneum in a closed system into a reservoir. Analysis was performed with CO2-laser-based photoacoustic spectroscopy and confirmed by a Fourier-transform infrared spectrum. The detected spectra were compared to the available spectra of known toxins. RESULTS: Samples from four laparoscopic sigmoid resections were analyzed. No relevant differences were noted regarding patient and operation characteristics. The gas samples were stable over time proven by congruent control measurements as late as 24 h after sampling. The absorption spectra differed considerably between the patients. One broad absorption line at 100 ppm indicating H2O and several unknown molecules were detected. With a sensitivity of alpha min ca 10-5 cm-1 no known toxic substances like phenol or indole were identified. CONCLUSION: The use of a vessel sealing device during laparoscopic surgery does not produce known toxic substances in relevant quantity. Further studies are needed to identify unknown molecules and to analyze gas emission under various conditions.

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To assess the role of vasopressin (AVP) in congestive heart failure (CHF), we investigated 10 patients with CHF refractory to conventional treatment, before and 60 minutes after intravenous administration of 5 micrograms/kg of d(CH2)5Tyr(Me)AVP, a specific antagonist of AVP at the vascular receptor level. Heart rate, systemic arterial pressure, pulmonary arterial pressure, pulmonary capillary wedge pressure, cardiac index by thermodilution, and cutaneous blood flow by laser-Doppler technique were measured. In 9 patients there was no significant hemodynamic and cutaneous blood flow response to the AVP antagonist. Plasma AVP was 2.3 +/- 0.8 pg/ml and plasma osmolality 284 +/- 14 mosm/kg H2O. The tenth patient had the most severe CHF. His plasma AVP was 55 pg/ml and plasma osmolality 290 mosm/kg. He responded to the AVP antagonist with a marked decrease in systemic arterial pressure from 115/61 to 79/41 mm Hg, in pulmonary arterial pressure from 58/31 to 33/13 mm Hg and in pulmonary capillary wedge pressure from 28 to 15 mm Hg. Simultaneously cardiac index increased from 1.1 to 2.21 X min-1 X m-2 and cutaneous blood flow rose 5-fold. Thus, most patients with CHF have only moderately elevated plasma AVP and its role in determining peripheral vascular resistance appears to be limited. AVP may become important in rare patients presenting with marked hemodynamic instability and very high plasma AVP.