Modelling the absorption and desorption of cadmium on paper pulp using kinetic approaches

The presence of toxic metals on paper pulp and the migration of these metals to food from the food package is receiving significant attention. The final exposure levels for consumers depend on two main processes. First the potential of metals to bind paper pulp during manufacture. Second, the metal potential to migrate from paper to food during storage and use. Binding and unbinding processes are modelled for cadmium kinetics through kinetic approaches. The cadmium concentration in paper pulp is estimated from the cadmium concentration in the water-pulp liquor during manufacture, the temperature, and contact time. Two food simulants have been employed for desorption studies, water and acetic solution (3%, w/w). As expected, under acidic conditions desorption is total and rapid (close to 100% desorption reached in a few minutes). However, the desorption of cadmium into the neutral food simulant depends on the initial cadmium concentration in the paper pulp, temperature and contact time. Surface response curves for each combination are presented. Temperature did not affect cadmium binding, but played a significant role for the desorption processes into the neutral food simulant. The proposed equations offer a good fitting of the experimental values, with p < 0.001 and residuals within a factor of 3 for over 99% of the measured data. These models allow estimations of the expected exposure levels in consumers, on the basis of manufacture and use conditions. Linking the expected exposure with toxicity thresholds, such as the admissible daily intake (ADI), would allow a scientific assessment of the maximum acceptable cadmium levels in water-pulp liquors during manufacture and in the final paper pulp on the basic of the use patterns of each food packaging material.     

Adsorption of atrazine from aqueous solution on heat treated kerolites

The adsorption of 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on heat treated kerolite samples at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400) and 600 degrees C (K-600) from aqueous solution at 25 degrees C has been studied. The evolution of surface properties of kerolite samples such as specific surface area and porosity after heat treatment was analysed. The clays were characterised by using usual techniques: FTIR spectroscopy, XRD diffraction, TG and DTG analysis, surface analysis and Hg porosimetry. The adsorption experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (K(f)) of the samples; K(f) values range from 468 mgkg(-1) for the K-110 sample up to 2291 mgkg(-1) for the K-600 sample. The values obtained for the removal efficiency (R), (percentage of pesticide removed), ranged from 48% for K-110 up to 78% for K-600. The adsorption experiments showed that the stronger heat treatment, the most effective adsorption of atrazine, so, as this type of clay is relatively plentiful, these activated samples might be used in order to remove this pesticide from water.     

Study on the formation and transport of ozone in relation to the air quality management and vegetation protection in Tenerife (Canary Islands)

An experimental study on the formation and transport of ozone in ambient air was performed in Tenerife (Canary Islands) in order to investigate the processes affecting ozone levels and air quality. The special features of Tenerife (prevalence of the trade wind pattern (NE), orography and the specific location of the local ozone sources) permit to quantify the role of the ‘long-range transport from northern latitudes' versus the ‘formation and transport of ozone downwind of the main urban areas' of Tenerife. Levels of O₃, NO₂ and O_X were monitored in different types of environments to achieve this purpose. The results showed that: (1) upwind of the urban areas ozone is mainly transported from the ocean by trade winds, (2) local ozone titration (by NO) and ozone replenishment from the ocean are the main causes of ozone variations in urban and suburban areas, and (3) photochemical ozone production occurs downwind of the urban areas. Photochemical production causes daylight O₃ and O_X levels downwind of urban areas to be frequently (60% and 35% days/year, respectively) higher than upwind of the urban sites (O₃ and O_X excess frequently in the range 5–20 ppbv). Due to the above processes, different daily ozone cycles occur in short distances (<30 km), with maximum O₃ levels during daylight or night depending on the site. Ozone phytotoxicity was assessed by calculating the AOT40 index upwind and downwind of the main urban areas. The critical value for the 5-day-AOT40 index was simultaneously exceeded at the two sites (few times/year) during long-range transport events. During the additional exceedances of the critical value downwind of the urban area, relatively high 5-day-AOT40 values were recorded upwind of the urban site. Thus, long-range transport from northern latitudes may produce relatively high 5-days-AOT40 levels in the oceanic boundary layer. These results are important for the protection of the large number of endemic plants in the Canaries. The conceptual model discussed in this study may be qualitatively applied to other islands which possess features similar to those of Tenerife.     

Lesions induced by 2,4-D and chlorpyrifos in tench (Tinca tinca L.): implication in toxicity studies

This study was undertaken to demonstrate the toxicity of two pesticides, chlorpyrifos (O,O-diethyl 0-3,5,6-trichloro-2-pyridyl phosphorothioate) and 2,4-D (Dichlorophenoxyacetic acid) to tench (Tinca tinca Linnaeus). Pathological samples of damaged tench kidney showing lesions were taken for statistical analysis in order to quantify different parameters. Analysis revealed differences in the action and/or action time of the two pesticides. These differences were more acute in the case of 2,4-D thereby indicating a greater toxicity. These differences, expressed by mathematical formulae of numerical variables, would enable, a priori, the identification of the responsible pesticide and the time of acting in new natural cases of poisonings with these substances.     

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.     

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.     

Copulatory plugs do not assure high first male fertilisation success: sperm displacement in a lizard

Sperm competition selects for opposing male defensive and offensive reproductive traits, and its outcome may be determined by the effectiveness to which one trait has evolved to out-compete the other. We tested the effectiveness of a first male plug physical interference with a second male insemination (defence) vs the effectiveness of plug and associated sperm displacement by a second male (offence) on the outcome of sperm competition in Iberian rock lizards. We conducted a double mating experiment where we compared the proportion of eggs per clutch fertilised by the same second males (against the same first males) when they copulated with females 30 min (first male plug adhered firmly inside the female cloaca) and 4 h (first male plug loosely adhered or shed from the female cloaca) after first males. We found that second males fertilised the majority of the eggs per clutch in the 30-min treatment, whereas fertilisations were equally shared between the two males in the 4-h treatment. These results show that plugs have little defensive effectiveness, and thus, do not assure high first male fertilisation success. Instead, sperm displacement appears to be associated with plug displacement. That is, because sperm embedded in first male plugs, and displaced from competition for fertilisations by second males, is expected to increase in number with decreasing time allowed for female sperm transport, second males thus enjoy higher fertilisation success. This study shows that offensive plug displacement out-competes plug defensive role in Iberian rock lizards. Moreover, it reveals sperm displacement as a novel sperm competition mechanism in reptiles.     

Loss of mating opportunities influences refuge use in the Iberian rock lizard,<Emphasis Type="Italic"> Lacerta monticola</Emphasis>

Because time spent in refuge may be costly if prey lose opportunities to forage, fight, or mate, prey allow predators to approach closer before beginning to flee when opportunity costs are high. Because the same opportunity costs may apply to refuge use as to escape, prey should make similar trade-offs between risk of emerging and cost of remaining in refuge. In the Iberian rock lizard, Lacerta monticola, we studied the effects of sex, reproductive season, speed of predator approach, and potential loss of mating opportunities on time spent in refuge following simulated predatory attacks. Lizards of both sexes adjusted refuge use to the level of risk by spending more time in refuge when approached rapidly than slowly. Females remained in refuge for equal times in the mating and postreproductive seasons, but males emerged sooner during the mating season, suggesting adjustment to a cost of lost opportunity to search for mates during the mating season. When a tethered female was nearby, males emerged from refuge earlier than if no female was present, indicating a trade-off between risk and mating opportunity. Approach speed affected emergence time when females were absent, but not when a female was present. Approach speed did not affect the probability that, after emerging, a male would return to court the female. For males that courted females intensely (bit them) before entering refuge, approach speed did not affect latency to emerge, but males that courted less intensely emerged sooner if approached slowly than rapidly. These findings show that males adjust the length of time spent in refuge to both risk of predation and reproductive cost of refuge use.Communicated by A. Mathis