Simultaneous estimation of effective and apparent diffusion coefficients in compacted bentonite

Effective diffusion coefficients (D(e)) are usually measured by means of "through-diffusion" experiments in which steady state is reached, and the "time-lag" methods are used to estimate the apparent diffusion coefficient (D(a)). For sorbing radionuclides (as caesium), the time needed to reach steady-state conditions is very large, and the precision in D(a) determinations is not satisfactory. In this paper, a method that allows determining simultaneously effective and apparent diffusion coefficients in compacted bentonite without reaching steady-state conditions is described. Basically, this method consists of an "in-diffusion" experiment in which the concentration profile in the bentonite sample is used to estimate D(a), and the temporal evolution of the solute concentration in the reservoir is used to estimate D(e). This method has several advantages over the typical "through-diffusion" experiments, in particular: (a) experiment duration is significantly shorter, (b) D(a) values are measured with greater precision and (c) it is not necessary to maintain a constant solute concentration in the reservoir. This new method has been used to estimate the effective and apparent diffusion coefficients for caesium in FEBEX bentonite and in order to validate it, the results have been compared with results previously obtained with standard methods. Experimental results have been satisfactorily modelled using a simple model of diffusion in porewater and the measured value of D(e)(Cs) is very similar to D(e)(HTO) in the same bentonite. There is no evidence of "surface diffusion" in FEBEX bentonite for caesium.     

Toxic by-products from the combustion of Kraft lignin

Lignin samples, sub-product in the Kraft process of cellulose from eucalyptus wood, were burnt in a laboratory scale furnace at different residence temperatures and with distinct fuel-rich atmospheres. The yields of CO, CO(2), eight light hydrocarbons (methane, ethylene, ethane, propylene, acetylene, butane, etc.) and 60 semi-volatile+volatile compounds (benzene, toluene, ethylbenzene, styrene, indene, naphthalene, dibenzofuran, phenanthrene, chrysene, etc.) were determined, with nominal reactor temperatures between 800 and 1100 degrees C and residence times of the volatiles evolved and formed between 4 and 7 s. The collection of the gases and volatiles evolved was carried out with a Tedlar bag and by XAD-4 resin respectively, comparing the data obtained in both cases. The emission factor (mg/kg) of the CO was between 2500 and 90000, and under the poor-oxygen atmosphere, the emission factors of many by-toxic products were greater than 100 mg/kg. A pyrolysis run was also performed, obtaining emission factors between 30 and 3000 mg/kg, facilitating its identification. The behaviour of different compounds in the combustion runs was discussed considering three groups in accordance with their stability vs. oxygen, and two groups vs. temperature.     

Oxidation of methane over palladium catalysts: effect of the support

This work is focused on the deep catalytic oxidation of methane over supported palladium catalysts. The influences of the metal loading, oxidation state of palladium, nature of supports, presence of promoters in the supports (for zirconia-based supports), and thermal stability have been studied experimentally. Catalysts were prepared by incipient wetness of commercially available supports with aqueous solutions of palladium nitrate. For gamma-alumina support, it was observed that the optimal amount of palladium is between 0.5% and 2%, with higher amounts leading to a loss in specific activity. Concerning the oxidation state of the catalyst, it is concluded that for all the supports tested in the present work, a reduction of the catalyst is not needed, yielding the same conversion at steady state catalysts reduced and oxidised. The thermal stability of various supported catalysts were also studied, zirconia supports being the most active. These supports, specially Y-modified zirconia support, do not suffer appreciable deactivation below 500 degrees C.     

Rapid regional recovery from sulfate and nitrate pollution in streams of the western Czech Republic--comparison to other recovering areas

Hydrochemical changes between 1991 and 2001 were assessed based on two synoptic stream surveys from the 820-km2 region of the Slavkov Forest and surrounding area, western Czech Republic. Marked declines of sulfate, nitrate, chloride, calcium and magnesium in surface waters were compared with other areas of Europe and North America recovering from acidification. Declines of sulfate concentration in the Slavkov Forest (-30 microeq L(-1) yr(-1)) were more dramatic than declines reported from other sites. However, these dramatic declines of strong acid anions did not generate a widespread increase of stream water pH in the Slavkov Forest. Only the most acidic streams experienced a slight increase of pH by 0.5 unit. An unexpected decline of stream water pH occurred in slightly alkaline streams.     

Comparison of supercritical fluid extraction and Soxhlet extraction for the determination of PCBs in seaweed samples

The efficiency of supercritical fluid extraction for the determination of 12 polychlorinated biphenyls from algae samples is compared to Soxhlet extraction. Analytical detection limits for the individual congeners ranged from 0.62 microgl(-1) to 19 microgl(-1). Recovery was tested for both methods using standard addition procedure. At maximum spike level of concentration, the mean recoveries were not significantly different (P>0.05) of all PCBs studied, with the exception of PCBs 28, 52, 77 and 169. Method precision for Soxhlet extraction (< or =3.9%) was slightly better than for SFE (< or =9.2%). Although both methods yield comparable results, SFE offers the advantage of detecting all PCBs studied at lower concentrations, reducing extraction time, and reducing the amount of solvents needed. The optimized methods were applied to the analysis of three real seaweed samples, except for PCB101 the concentrations of all PCBs were low or below the detection limits. The levels of PCB101 found in sample 1 were 6.6+/-0.54 ng g(-1) d.w., in sample 2 the levels were 8.2+/-0.86 ng g(-1) d.w. and in sample 3 they were 7.7+/-0.08 ng g(-1) d.w.     

Health-dependent vulnerability to predation affects escape responses of unguarded chinstrap penguin chicks

Predators may select more often to attack the more vulnerable prey or those with an inferior health status. Thus, prey should be able to assess their own vulnerability to predation and modify their antipredatory behavior accordingly. When approached by predator skuas, unguarded penguin chicks flee short distances, and usually aggregate in dense packs, but there is a clear interindividual variability in their responses under similar conditions. We hypothesized that this variability in escape responses might be related to the perceived vulnerability to predation of each individual chick. We simulated predator attacks to chinstrap penguin chicks and analyzed the sources of variation in their escape response, such as the presence of adults or the density of other chicks, and the sex, age, body condition, and health status of responding chicks. Chicks allowed shorter approach distances when they had a better health condition (i.e., a greater T-cell-mediated immunity, CMI), when they were younger, and when the density of adults around was higher. Sex and density of other chicks were not important. Similarly, chicks fled from the experimenter to longer distances when they had a lower CMI and when the density of adults was lower. Therefore, escape characteristics of chicks depended on the presence of adults that can deter predators and on the health-dependent vulnerability of chicks.     

Genome-size variation in bivalve molluscs determined by flow cytometry

Six of the nine described species of the mole crab genus Emerita are distributed in the Americas, two [E. analoga (Stimpson, 1857) and E. rathbunae Schmitt, 1935] on the west coast, and four [E. benedicti Schmitt, 1935, E. brasiliensis Schmitt, 1935, E. portoricensis Schmitt, 1935 and E. talpoida (Say, 1817)] on the east. The presence of an extended planktonic larval stage in all Emerita species suggests high dispersal potential and the possibility of extensive gene flow among conspecific populations. Two taxa were sampled to study the extent of gene flow between widely separated conspecific populations: E. analoga (California and Chile) and E. talpoida (Massachusetts, South Carolina, and the west coast of Florida), while all other taxa were characterized from a single location. Portions of two mitochondrial genes, cytochrome oxidase I (COI) and 16S ribosomal RNA (16S rRNA) were sequenced. For data analysis, approximately 500 bp (COI) and 400 bp (16S rRNA) were examined. Estimated genetic divergence of 5.41% in COI between E. talpoida populations sampled from the Gulf of Mexico and the Atlantic coast, and 3.47% between E. analoga sampled in Chile and California, indicates that in both cases there has been no recent gene flow between disjunct populations. Additional molecular and morphological studies are necessary to decide whether disjunct populations should be accorded specific status. We predict that many marine invertebrates with antitropical distributions similar to E. analoga may consist of sibling species. In contrast to relationships inferred earlier from distribution patterns, parsimony analyses of both COI and 16S rRNA data yield similar phylogenetic trees in which E. analoga is separated from a clade composed of other species in the Americas; a bootstrap value (67%) in the COI inferred tree marginally supports the separation, but the same tree topology with a higher bootstrap value (84%) is obtained with 16S rRNA sequence data. Genetic divergence among the taxa indicates that the Emerita species constitute an old group and that distribution of species has been modified by past climatic and geological events.     

Removal of the herbicide amitrole from water by anodic oxidation and electro-Fenton

Here we demonstrate that an aqueous solution of the herbicide amitrole can be completely depolluted at pH 3.0 by anodic oxidation and electro-Fenton process. Anodic oxidation gives faster degradation with a boron-doped diamond anode than with a Pt anode. Electro-Fenton with a Pt anode and 1 mmol l ^–1 Fe²⁺ as catalyst yields the quickest depollution. Amitrole decay always follows a pseudo first-order reaction. NO₃^– and NH₄⁺ are accumulated in the medium during mineralization, although volatile N-products are also formed. These environmentally friendly electrochemical treatments could be applied to the remediation of wastewaters containing amitrole.     

Regulation of fructose-2,6-bisphosphate content in mantle tissue of the sea musselMytilus galloprovincialis

6-phosphofructo-2-kinase (PFK-2) from the mantle of the sea musselMytilus galloprovincialis Lmk, collected from the Ría de Arosa (NW Spain) in 1990, was purified 550-fold by extraction and sequential affinity chromatography on Affi-gel Blue and ATP-agarose columns. The enzyme was a dimer with a native molecular weight of 100 kilodaltons (KDa) and a subunitM _r of 53 KDa. PFK-2 activity is dependent on the presence of P_i. At physiological P_i concentrations, the enzyme exhibits hyperbolic kinetics with both ATP and Fru-6-P, withK _m values of 0.62 and 0.37 mM respectively. In vivo, PFK-2 activity is limited by the concentration of Fru-6-P which is low in comparison with theK _m for this substrate. Citrate and PEP inhibited PFK-2 activity.     

Chloroacetic acids in environmental processes

The fate of chloroacetic acids (CAA) in forest soils was studied using radio-indicator methods. We showed that chloroacetic acids are both microbially degraded and simultaneously formed by chloroperoxidase-mediated chlorination of acetic and humic acids. The degree of biodegradation of chloroacetic acids in soil depends on their concentration. Dichloroacetic acid (DCA) is degraded faster than trichloroacetic acid (TCA). Chlorination of acetic acid led to a fast formation of dichloroacetic acid, whereas chlorination of humic acids gave rise to trichloroacetic acid. Both processes lead to a steady state in soil, participate in the chlorine cycle and possibly also in decomposition of organic matter in forest ecosystems.