947 resultados para tannin adsorption
Resumo:
We have studied the adsorption process of non-Brownian particles on a line. Our work differs from previously proposed models in that we have incorporated hydrodynamic interactions between the incoming particles and the preadsorbed particles as well as the surface. We then numerically analyze the effect of these interactions on quantities related to the adsorption process. Comparing our model to the ballistic deposition model (BM) shows a significant discrepancy in the pair correlation function. These results can explain some differences between recent experiments and BM predictions. Finally, the limitations of the applicability of BM are addressed.
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The Mehlich-1 (M-1) extractant and Monocalcium Phosphate in acetic acid (MCPa) have mechanisms for extraction of available P and S in acidity and in ligand exchange, whether of the sulfate of the extractant by the phosphate of the soil, or of the phosphate of the extractant by the sulfate of the soil. In clayey soils, with greater P adsorption capacity, or lower remaining P (Rem-P) value, which corresponds to soils with greater Phosphate Buffer Capacity (PBC), more buffered for acidity, the initially low pH of the extractants increases over their time of contact with the soil in the direction of the pH of the soil; and the sulfate of the M-1 or the phosphate of the MCPa is adsorbed by adsorption sites occupied by these anions or not. This situation makes the extractant lose its extraction capacity, a phenomenon known as loss of extraction capacity or consumption of the extractant, the object of this study. Twenty soil samples were chosen so as to cover the range of Rem-P (0 to 60 mg L-1). Rem-P was used as a measure of the PBC. The P and S contents available from the soil samples through M-1 and MCPa, and the contents of other nutrients and of organic matter were determined. For determination of loss of extraction capacity, after the rest period, the pH and the P and S contents were measured in both the extracts-soils. Although significant, the loss of extraction capacity of the acidity of the M-1 and MCPa extractants with reduction in the Rem-P value did not have a very expressive effect. A “linear plateau” model was observed for the M-1 for discontinuous loss of extraction capacity of the P content in accordance with reduction in the concentration of the Rem-P or increase in the PBC, suggesting that a discontinuous model should also be adopted for interpretation of available P of soils with different Rem-P values. In contrast, a continuous linear response was observed between the P variables in the extract-soil and Rem-P for the MCPa extractor, which shows increasing loss of extraction capacity of this extractor with an increase in the PBC of the soil, indicating the validity of the linear relationship between the available S of the soil and the PBC, estimated by Rem-P, as currently adopted.
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ABSTRACT Intrinsic equilibrium constants of 17 representative Brazilian Oxisols were estimated from potentiometric titration measuring the adsorption of H+ and OH− on amphoteric surfaces in suspensions of varying ionic strength. Equilibrium constants were fitted to two surface complexation models: diffuse layer and constant capacitance. The former was fitted by calculating total site concentration from curve fitting estimates and pH-extrapolation of the intrinsic equilibrium constants to the PZNPC (hand calculation), considering one and two reactive sites, and by the FITEQL software. The latter was fitted only by FITEQL, with one reactive site. Soil chemical and physical properties were correlated to the intrinsic equilibrium constants. Both surface complexation models satisfactorily fit our experimental data, but for results at low ionic strength, optimization did not converge in FITEQL. Data were incorporated in Visual MINTEQ and they provide a modeling system that can predict protonation-dissociation reactions in the soil surface under changing environmental conditions.
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The Radiello Passive Air Sampler is one of the latest innovations developed for the sampling of pollutants in the air by passive headspace. It has been reported that its properties allow an enhanced sensitivity, reproducibility and adsorption capacity. It therefore appears to be of interest in the extraction of potential residues of ignitable liquids present in fire debris when arson is suspected. A theoretical approach and several laboratory tests have made it possible to precisely characterize in a forensic perspective the potential of the device in extracting and concentrating the vapors of ignitable liquids found in fire debris. Despite some advantages, the Radiello device appears to be less efficient than traditional axial symmetry samplers.
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A novel and simple procedure for concentrating adenoviruses from seawater samples is described. The technique entails the adsorption of viruses to pre-flocculated skimmed milk proteins, allowing the flocs to sediment by gravity, and dissolving the separated sediment in phosphate buffer. Concentrated virus may be detected by PCR techniques following nucleic acid extraction. The method requires no specialized equipment other than that usually available in routine public health laboratories, and due to its straightforwardness it allows the processing of a larger number of water samples simultaneously. The usefulness of the method was demonstrated in concentration of virus in multiple seawater samples during a survey of adenoviruses in coastal waters.
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Exposure to human pathogenic viruses in recreational waters has been shown to cause disease outbreaks. In the context of Article 14 of the revised European Bathing Waters Directive 2006/7/EC (rBWD, CEU, 2006) a Europe-wide surveillance study was carried out to determine the frequency of occurrence of two human enteric viruses in recreational waters. Adenoviruses were selected based on their near-universal shedding and environmental survival, and noroviruses (NoV) selected as being the most prevalent gastroenteritis agent worldwide. Concentration of marine and freshwater samples was done by adsorption/elution followed by molecular detection by (RT)-PCR. Out of 1410 samples, 553 (39.2%) were positive for one or more of the target viruses. Adenoviruses, detected in 36.4% of samples, were more prevalent than noroviruses (9.4%), with 3.5% GI and 6.2% GII, some samples being positive for both GI and GII. Of 513 human adenovirus-positive samples, 63 (12.3%) were also norovirus-positive, whereas 69 (7.7%) norovirus-positive samples were adenovirus-negative. More freshwater samples than marine water samples were virus-positive. Out of a small selection of samples tested for adenovirus infectivity, approximately one-quarter were positive. Sixty percent of 132 nested-PCR adenovirus-positive samples analysed by quantitative PCR gave a mean value of over 3000 genome copies per L of water. The simultaneous detection of infectious adenovirus and of adenovirus and NoV by (RT)PCR suggests that the presence of infectious viruses in recreational waters may constitute a public health risk upon exposure. These studies support the case for considering adenoviruses as an indicator of bathing water quality.
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SEVERAL attempts have been made to show the specific localisation in vivo of anti-tumour antibodies. Most of these studies, however, either in experimental animals1,2 or in humans3 were performed with antibodies obtained by adsorption and elution from poorly characterised crude tumour fractions.
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Interaction models of atomic Al with Si4H9, Si4H7, and Si6H9 clusters have been studied to simulate Al chemisorption on the Si(111) surface in the atop, fourfold atop, and open sites. Calculations were carried out using nonempirical pseudopotentials in the framework of the ab initio Hartree-Fock procedure. Equilibrium bond distances, binding energies for adsorption, and vibrational frequencies of the adatoms are calculated. Several basis sets were used in order to show the importance of polarization effects, especially in the binding energies. Final results show the importance of considering adatom-induced relaxation effects to specify the order of energy stabilities for the three different sites, the fourfold atop site being the preferred one, in agreement with experimental findings.
Resumo:
By means of the ab initio cluster-model approach, we present theoretical evidence for two different mechanisms of bonding of atomic Al to Si(111). On the atop site (T1) the interaction of atomic Al to Si(111) is characteristic of an ionic bond whereas interaction above the threefold eclipsed site (T4) leads to the formation of a typical covalent bond. Moreover, both sites have a similar interaction energy if electronic correlation effects are included. While the conclusions regarding the nature of the chemisorption bond in the two sites do not depend either on the cluster-model size, the kind of embedding hydrogen atoms used, or the quality of the wave function (Hartree-Fock or configuration interaction), the chemisorption energy depends strongly on the wave function used. In fact, inclusion of correlation energy is necessary to properly describe the interaction energies.
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In addition to the importance of sample preparation and extract separation, MS detection is a key factor in the sensitive quantification of large undigested peptides. In this article, a linear ion trap MS (LIT-MS) and a triple quadrupole MS (TQ-MS) have been compared in the detection of large peptides at subnanomolar concentrations. Natural brain natriuretic peptide, C-peptide, substance P and D-Junk-inhibitor peptide, a full D-amino acid therapeutic peptide, were chosen. They were detected by ESI and simultaneous MS(1) and MS(2) acquisitions. With direct peptide infusion, MS(2) spectra revealed that fragmentation was peptide dependent, milder on the LIT-MS and required high collision energies on the TQ-MS to obtain high-intensity product ions. Peptide adsorption on surfaces was overcome and peptide dilutions ranging from 0.1 to 25 nM were injected onto an ultra high-pressure LC system with a 1 mm id analytical column and coupled with the MS instruments. No difference was observed between the two instruments when recording in LC-MS(1) acquisitions. However, in LC-MS(2) acquisitions, a better sensitivity in the detection of large peptides was observed with the LIT-MS. Indeed, with the three longer peptides, the typical fragmentation in the TQ-MS resulted in a dramatic loss of sensitivity (> or = 10x).
Resumo:
Summary Artificial radionuclides were released in the environment during the atmospheric nuclear weapon tests and after accidental events involving nuclear industries. As a primary receptor of the deposition, the soil is a very sensitive compartment and understanding the interaction and migration of radionuclides within soils allows the development of scenario for the contamination risk of the population and of the environment. Most available field studies on radionuclides in soils only concern one or two isotopes, mostly 137Cs, and few physico-chemical soil parameters. The purpose of this study was a broader understanding of the radioecology of an Alpine valley. In a first part, we aimed to describe the depth distribution of 137Cs, 90Sr, 239+240Pu, and 241Am within different alpine soils and to identify some stable elements as indicators for accumulating layers. In the central part of the study, the goal was to investigate the repartition of ^Sr and 239Pu between the truly dissolved fraction and the colloidal fraction of the soil solutions and to identify the nature of colloids involved in the adsorption of ^Sr and 239Pu. These results were integrated in an "advection- sorption" transport model seeking to explain the migration of 239Pu and 90Sr within the soils and to assess the importance of colloidal transport for these two isotopes. A further aspect studied was the role of the competition between the radioisotopes (137Cs and 90Sr) and their stable chemical analogues (K and Ca) with respect to plant uptake by different plant species. The results on the depth distribution within the soils showed that 137Cs was mostly retained in the topsoil, to the exception of an organic-rich soil (Histosol 2) receiving important surface runoff, where migration down to a depth of 30 cm was observed. 137Cs depth distribution within the soils was similar to unsupported 210Pb depth distribution. The plant uptake of 137Cs clearly depended on the concentration of exchangeable potassium in the soils. Moreover, we showed that the 137Cs uptake by certain species of the taxonomic orders Poales and Rosales was more sensitive to the increase in exchangeable Κ compared to other orders. Strontium-90 was much more mobile in the soils than 137Cs and depth migration and accumulation in specific AI- and Fe-rich layers were found down to 30 cm. Copper and Ni showed accumulations in these same layers, indicating their potential to be used as indicators for the migration of ^Sr within the soils. In addition, we observed a 90Sr activity peak in the topsoil that can be attributable to recycling of 90Sr by plant uptake. We demonstrated for the first time that a part of 90Sr (at least 40%) was associated with the colloids in organic-rich soil solutions. Therefore, we predict a significant effect of the colloidal migration of ^Sr in organic-rich soil solutions. The plant uptake results for 90Sr indicated a phylogenetic effect between Non-Eudicot and Eudicots: the order Poales concentrating much less 90Sr than Eudicots do. Moreover, we were able to demonstrate that the sensitivity of the 90Sr uptake by 5 different Alpine plant species to the amount of exchangeable Ca was species-independent. Plutonium and 241Am accumulated in the second layer of all soils and only a slight migration deeper than 20 cm was observed. Plutonium and 241Am showed a similar depth distribution in the soils. The model results suggested that the present day migration of 239Pu was very slow and that the uptake by plants was negligible. 239Pu activities between 0.01 to 0.08 mBq/L were measured in the bulk soil solutions. Migration of 239Pu with the soil solution is dominated by colloidal transport. We reported strong evidences that humic substances were responsible of the sorption of 239Pu to the colloidal fraction of the soil solutions. This was reflected by the strong correlation between 239Pu concentrations and the content of (colloidal) organic matter in the soil solution. Résumé Certains radioéléments artificiels ont été disséminés dans l'environnement suite aux essais atmosphériques de bombes nucléaires et suite à des accidents impliquant les industries nucléaires. En tant que récepteur primaire de la déposition, le sol est un compartiment sensible et des connaissances sur les interactions et la migration des radioéléments dans le sol permettent de développer des modèles pour estimer la contamination de la population et de l'environnement. Actuellement, la plupart des études de terrain sur ce sujet concernent uniquement un ou deux radioéléments, surtout le 137Cs et peu d'études intègrent les paramètres du sol pour expliquer la migration des radioéléments. Le but général de cette étude était une compréhension étendue de la radio-écologie d'une vallée alpine. Notre premier objectif était de décrire la distribution en profondeur de 137Cs, ^Sr, 239+240pu et 241Am dans différents sols alpins en relation avec des éléments stables du sol, dans le but d'identifier des éléments stables qui pourraient servir d'indicateurs pour des horizons accumulateurs. L'objectif de la deuxième partie, qui était la partie centrale de l'étude, était d'estimer le pourcentage d'activité sous forme colloïdale du 239Pu et du 90Sr dans les solutions des sols. De plus nous avons déterminé la nature des colloïdes impliqués dans la fixation du ^Sr et 239Pu. Nous avons ensuite intégré ces résultats dans un modèle de transport développé dans le but de décrire la migration du 239Pu et 90Sr dans le sol. Finalement, nous avons étudié l'absorption de 137Cs et 90Sr par les plantes en fonction de l'espèce et de la compétition avec leur élément analogue stable (K et Ca). Les résultats sur la migration en profondeur du 137Cs ont montré que ce radioélément était généralement retenu en surface, à l'exception d'un sol riche en matière organique dans lequel nous avons observé une nette migration en profondeur. Dans tous les sols, la distribution en profondeur du 137Cs était corrélée avec la distribution du 210Pb. L'absorption du 137Cs par les plantes, était dépendante de la concentration en Κ échangeable dans le sol, le potassium étant un compétiteur. De plus, nous avons observé que les espèces ne réagissaient pas de la même manière aux variations de la concentration de Κ échangeable. En effet, les espèces appartenant aux ordres des Poales et des Rosales étaient plus sensibles aux variations de potassium échangeable dans le sol. Dans tous les sols Le 90Sr était beaucoup plus mobile que le 137Cs. En effet, nous avons observé des accumulations de 90Sr dans des horizons riches en Fe et Al jusqu'à 30 cm de profondeur. De plus, le Cu et le Ni montraient des accumulations dans les mêmes horizons que le 90Sr, indiquant qu'il pourrait être possible d'utiliser ces deux éléments comme analogues pour la migration du 90Sr. D'après le modèle développé, le pic de 90Sr dans les premiers centimètres du sol peut être attribué à du recyclage par les plantes. Le 90Sr en solution était principalement sous forme dissoute dans des solutions de sols peu organique (entre 60 et 100% de 90Sr dissous). Par contre, dans des solutions organiques, un important pourcentage de 90Sr (plus de 40%) était associé aux colloïdes. La migration colloïdale du 90Sr peut donc être significative dans des solutions organiques. Comme pour le 137Cs, l'absorption du 90Sr par les plantes dépendait de la concentration de son analogue chimique dans la fraction échangeable du sol. Par contre, les espèces de plantes étudiées avaient la même sensibilité aux variations de la concentration du calcium échangeable. Le plutonium et l'américium étaient accumulés dans le deuxième horizon du sol et nous avons observé seulement une faible migration plus profondément que 20 cm. Selon le modèle, la migration actuelle du plutonium est très lente et l'absorption par les plantes semble négligeable. Nous avons mesuré entre 0.01 et 0.08 mBq/L de 239Pu dans les solutions de sol brutes. La migration du plutonium par la solution du sol est due principalement aux colloïdes, probablement de nature humique. Résumé grand public Dans les années 1950 à 1960, l'environnement a été contaminé par des éléments radioactifs (radioéléments) artificiels provenant des essais des armes atomiques et de l'industrie nucléaire. En effet, durant ces années, les premiers essais de bombes atomiques se faisaient dans l'atmosphère, libérant de grandes quantités d'éléments radioactifs. De plus certains accidents impliquant l'industrie nucléaire civile ont contribué à la dissémination d'éléments radioactifs dans l'environnement. Ce fut par exemple le cas de l'accident de la centrale atomique de Tchernobyl en 1986 qui a causé une importante contamination d'une grande partie de l'Europe par le 137Cs. Lorsqu'ils sont libérés dans l'atmosphère, les radioéléments sont dispersés et transportés par les courants atmosphériques, puis peuvent être déposés dans l'environnement, principalement par les précipitations. Une fois déposés sur le sol, les radioéléments vont interagir avec les composants du sol et migrer plus ou moins vite. La connaissance des interactions des éléments radioactifs avec le sol est donc importante pour prédire les risques de contamination de l'environnement et de l'homme. Le but général de ce travail était d'évaluer la migration de différents éléments radioactifs (césium-137, strontium-90, plutonium et américium-241) à travers le sol. Nous avons choisi un site d'étude en milieu alpin (Val Piora, Tessin, Suisse), contaminé en radioéléments principalement par les retombées de l'accident de Tchernobyl et des essais atmosphériques de bombes atomiques. Dans un premier temps, nous avons caractérisé la distribution en profondeur des éléments radioactifs dans le sol et l'avons comparée à divers éléments stables. Cette comparaison nous a permit de remarquer que le cuivre et le nickel s'accumulaient dans les mêmes horizons du sol que le strontium-90 et pourraient donc être utilisés comme analogue pour la migration du strontium-90 dans les sols. Dans la plupart des sols étudiés, la migration du césium-137, du plutonium et de l'américium-241 était lente et ces radioéléments étaient donc accumulés dans les premiers centimètres du sol. Par contre, le strontium-90 a migré beaucoup plus rapidement que les autres radioéléments si bien qu'on observe des accumulations de strontium-90 à plus de 30 cm de profondeur. Les radioéléments migrent dans la solution du sol soit sous forme dissoute, soit sous forme colloïdale, c'est-à-dire associés à des particules de diamètre < Ιμηι. Cette association avec des colloïdes permet à des radioéléments peu solubles, comme le plutonium, de migrer plus rapidement qu'attendu. Nous avons voulu savoir quelle était la part de strontium-90 et plutonium associés à des colloïdes dans la solution du sol. Les résultats ont montré que le plutonium en solution était principalement associé à des colloïdes de type organique. Quant au strontium-90, ce dernier était en partie associé à des colloïdes dans des solutions de sol riches en matière organique, par contre, il était principalement sous forme dissoute dans les solutions de sol peu organiques. L'absorption de radioéléments par les plantes représente une voie importante pour le transfert vers la chaîne alimentaire, par conséquent pour la contamination de l'homme. Nous avons donc étudié le transfert du césium-137 et du strontium-90 de plusieurs sols vers différentes espèces de plantes. Les résultats ont montré que l'absorption des radioéléments par les plantes était liée à la concentration de leur analogue chimique (calcium pour le strontium-90 et potassium pour le césium- 137) dans la fraction échangeable du sol. De plus certaines espèces de plantes accumulent significativement moins de strontium-90.
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In the present work, the physical and chemical characteristics in three stages of maturation of sapota (Manilkara zapota L.P. Royen) fruit were studied as well as its post-harvest behavior during storage at ambient and refrigerated conditions. With the advance of maturation, the concentration of the reducing sugars increased while the total acidity and tannin contents decreased. The fruits which did not have their pedicel removed during the post-harvest presented the storage time superior when compared with the fruits having their pedicels removed. The fruits stored under refrigeration had higher weight retention as compared to the fruits stored under ambient conditions.
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The aim of this work is to present a new concept, called on-line desorption of dried blood spots (on-line DBS), allowing the direct analysis of a dried blood spot coupled to liquid chromatography mass spectrometry device (LC/MS). The system is based on an inox cell which can receive a blood sample (10 microL) previously spotted on a filter paper. The cell is then integrated into LC/MS system where the analytes are desorbed out of the paper towards a column switching system ensuring the purification and separation of the compounds before their detection on a single quadrupole MS coupled to atmospheric pressure chemical ionisation (APCI) source. The described procedure implies that no pretreatment is necessary in spite the analysis is based on whole blood sample. To ensure the applicability of the concept, saquinavir, imipramine, and verapamil were chosen. Despite the use of a small sampling volume and a single quadrupole detector, on-line DBS allowed the analyses of these three compounds over their therapeutic concentrations from 50 to 500 ng/mL for imipramine and verapamil and from 100 to 1000 ng/mL for saquinavir. Moreover, the method showed good repeatability with relative standard deviation (RSD) lower than 15% based on two levels of concentration (low and high). Function responses were found to be linear over the therapeutic concentration for each compound and were used to determine the concentrations of real patient samples for saquinavir. Comparison of the founded values with those of a validated method used routinely in a reference laboratory showed a good correlation between the two methods. Moreover, good selectivity was observed ensuring that no endogenous or chemical components interfered with the quantitation of the analytes. This work demonstrates the feasibility and applicability of the on-line DBS procedure for bioanalysis.
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Background: Chemoembolization is used to treat liver malignancies. However recurrence occurs frequently, possibly because of neoangiogenesis triggered by ischemia caused by the embolic agent. In this context, the combination of an embolic agent with an anti-angiogenic drug seems appealing. This study characterizes the in vitro loading and release profile of sunitinib eluting beads of different sizes and their pharmacokinetic profile in a rabbit model. Methods: 70-150 μm and 100-300 μm drug eluting beads (DC Bead, Biocompatibles UK) were loaded by incubation in a sunitinib hydrochloride solution. Drug was quantified by spectrophotometry at 430 nm. Drug release was measured over one-week periods and normalized using an internal standard in 30% ethanol in NaCl 0.9%. New-Zealand white rabbits were used. Eight animals received 0.2 ml of 100-300 μm DC Bead loaded with 6 mg of sunitinib in the hepatic artery (group 1) and 4 animals received 6 mg of sunitinib p.o. (group 2). Half of the animals were sacrificed after 6 hours and half after24 hours. Liver enzymes were measured at 0, 6 and 24 hours in both groups. Plasmatic sunitinib concentration was determined by tandem mass spectroscopy (LC MS/MS) at 0, 1, 2, 3, 4, 5, 6 and 24 hours. At sacrifice, the livers were harvested and sunitinib concentration in liver tissue was assessed by LC MS/MS. Results: High drug loading was obtained for both microsphere bead sizes. Particle shrinking was observed with adsorption of sunitinib. Almost complete release of sunitinib was detected under physiological conditions, with very similar release for 70-150 μm and 100-300 μm (t50%=1.2 h) DC Bead. Conclusions: Sunitinib eluting beads are well tolerated by rabbits when administered in the hepatic artery. No unexpected toxicity was observed. Very high drug concentration can be obtained at the site of embolization with minimal systemic passage.
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In order to detect fluctuations in ruminal microbial populations due to forage tannins using 16S ribosomal RNA (rRNA) probes, recovery of intact rRNA is required. The objective of this work was to evaluate the effect of polyethylene glycol (PEG) and polyvinylpirrolidone (PVP) on extraction of bacterial rRNA, in the presence of tannins from tropical legume forages and other sources, that hybridize with oligonucleotide probes. Ruminococcus albus 8 cells were exposed to 8 g/L tannic acid or 1 g/L condensed tannins extracted from Acacia angustissima, banana (Musa sp.) skin, Desmodium ovalifolium, red grape (Vitis vinifera) skin and Inga edulis, or no tannins. Cells were rinsed with Tris buffer pH 7 containing either 8% PEG or 6% PVP prior to cell lysis. Total RNA samples rinsed with either PEG or PVP migrated through denaturing agarose gels. The 16S rRNA bands successfully hybridized with a R. albus species-specific oligonucleotide probe, regardless of tannin source. The effect of rinsing buffers on the density of 16S rRNA bands, as well as on the hybridization signals was compared. There were significant effects (P<0.01) when the controls were compared to either buffer treatments due to tannin type, buffer used and the interaction of tannin type and buffer. The significant interaction indicates the influence of tannin type on the parameters evaluated.