Kinetic of formation for single carbon dioxide and mixed carbon dioxide and tetrahydrofuran hydrates in water and sodium chloride aqueous solution

A laboratory-scale reactor system is built and operated to measure the kinetic of formation for single and mixed carbon dioxide–tetrahydrofuran hydrates. The T-cycle method, which is used to collect the kinetic data, is briefly discussed. For single carbon dioxide hydrate, the induction time decreases with the increase of the initial carbon dioxide pressure up to 2.96 MPa. Beyond this pressure, the induction time is becoming relatively constant with the increase of initial carbon dioxide pressure indicating that the liquid phase is completely supersaturated with carbon dioxide. Experimental results show that the inclusion of tetrahydrofuran reduces the induction time required for hydrate formation. These observations indicate hydrate nucleation process and onset growth are more readily to occur in the presence of tetrahydrofuran. In contrast, the presence of sodium chloride prolongs the induction time due to clustering of water molecules with the ions and the salting-out effects. It is also shown that the degree of subcooling required for hydrate formation is affected by the presence of tetrahydrofuran and sodium chloride in the hydrate forming system. The presence of tetrahydrofuran in the hydrate system significantly reduces the amount of carbon dioxide uptake. The apparent rate constant, k, for those systems are reported.     

Sub-tropical urban environment affecting content and composition of non-structural carbohydrates of Lolium multiflorum ssp. italicum cv. Lema

This study analyzed the relationship between environmental factors, especially air pollution and climatic conditions, and non-structural carbohydrates (NSC) in plants of Lolium multiflorum exposed during 10 consecutive periods of 28 days at a polluted site (Congonhas) and at a reference site in São Paulo city (Brazil). After exposure, NSC composition and leaf concentrations of Al, Fe, Cu, Zn, Pb and Cd were measured. The seasonal pattern of NSC accumulation was quite similar in both sites, but plants at Congonhas showed higher concentrations of these compounds, especially fructans of low and medium degree of polymerization. Regression analysis showed that NSC in plants growing at the polluted site were explained by variations on temperature and leaf concentration of Fe (positive effect), as well as relative humidity and particulate material (negative effect). NSC in the standardized grass culture, in addition to heavy metal accumulation, may indicate stressing conditions in a sub-tropical polluted environment.     

Different compensatory mechanisms in two metal-accumulating aquatic macrophytes exposed to acute cadmium stress in outdoor artificial lakes

Mechanisms underlying cadmium (Cd) detoxification were compared in two aquatic macrophytes commonly used in phytoremediation, namely Pistia stratiotes L. and Eichhornia crassipes (Mart.) Solms. To simulate Cd pollution in the open environment, plants growing in outdoor artificial lakes were exposed for 21d to either 25 or 100microM Cd, in two consecutive years. Toxicity symptoms were absent or mild in both species. Metal accumulation was much higher in the roots of P. stratiotes, whereas in E. crassipes a comparatively higher fraction was translocated to the leaves. In both species, Cd was neither included in phenolic polymers or Ca-oxalate crystals, nor altered the levels of Cd-complexing organic acids. Glutathione levels were constitutively remarkably higher and much more responsive to Cd exposure in P. stratiotes than in E. crassipes. Abundant phytochelatin synthesis occurred only in P. stratiotes, both in roots and in leaves. In E. crassipes, on the other side, the constitutive levels of some antioxidant enzymes and ascorbate were higher and more responsive to Cd than in P. stratiotes. Thus, in these two aquatic plants grown in the open, different detoxification mechanisms might come into play to counterbalance Cd acute stress.     

Polybrominated diphenyl ether in sewage sludge in Germany

Sewage sludge samples from 11 municipal waste water treatment plants in Germany were collected from March 2002 to June 2003. Total Tri- to HpBDE concentrations (sum of significant congeners BDE 28, 47, 99, 153, 154 and 183) ranged from 12.5 to 288 (median 108) and DeBDE (BDE 209) concentrations from 97.1 to 2217 (median 256) ng/gd.m. BDE 209 dominated the congener profile. A significant change of the Tri- to HpBDE congener profile (% of total BDE 28, 47, 99, 153, 154, 183 without 209) in sludge from different stages of the waste water treatment process (primary sludge, secondary excess sludge and (dewatered) digested sludge), indicating a degradation of DeBDE to these congeners, was not observed.     

Whole-mount in situ TUNEL method revealed ectopic pattern of apoptosis in cadmium treated naupliar larvae of barnacle (Balanus amphitrite Darwin)

The effect of cadmium on stage II naupliar larvae of barnacle (Balanus amphitrite Darwin) was investigated. Barnacle larvae were exposed to 0-15 microM CdCl(2) for 24 h. Apoptotic cells were stained by the terminal deoxyribonucleotidyl transferase mediated dUTP nick end labelling (TUNEL) method. Incidence of apoptosis, as measured by numbers of animals with ectopic pattern of apoptosis as well as numbers of apoptotic cells per animal, was assessed using confocal microscopy. An increase in incidence of apoptosis was observed in the experimental animals with an increase in cadmium concentration. Mortality increased, and motility decreased, when barnacle larvae were exposed to an increasing concentration of cadmium. The relationship between the occurrence of apoptosis and swimming behaviour was investigated in larvae exposed to 10 microM CdCl(2). Significant increases in apoptosis were detected in the non-motile and dead nauplii. This study suggested that whole-mount in situ TUNEL method may be used to study increased occurrence of apoptotic cells in crustacean larvae.     

Experimental support for the use of egg uniformity in parasite egg discrimination by cuckoo hosts

Common cuckoo (Cuculus canorus) parasitism drastically reduces the reproductive success of their hosts and selects for host discrimination of cuckoo eggs. In a second stage of anti-parasite adaptation, once cuckoos can lay eggs that mimic those of their hosts, a high uniformity of host egg appearance within a clutch may favour cuckoo egg discrimination. Comparative evidence provides indirect support for this hypothesis although experimental support is currently lacking. Here, we studied the effect of experimentally decreased uniformity of host egg appearance on cuckoo egg discrimination by great reed warbler (Acrocephalus arundinaceus) hosts in a population in which long-term cuckoo parasitism has led to high levels of cuckoo–host egg mimesis. We manipulated host clutch uniformity by adding extra spots to fresh host eggs just after they were laid. Rejection of non-mimetic experimental eggs added to these nests was compared with those in control nests in which uniformity was not altered. Previously, by over-painting real spots in a control group of nests, we showed a negligible effect of our paints on hosts’ perception of their eggs. We show that for the great reed warbler, non-mimetic experimental eggs were relatively more tolerated in experimental nests, i.e. with lower uniformity (40%) than in control nests (5%). This is the first experimental study, to our knowledge, which demonstrates a reduced discrimination of foreign eggs as a consequence of an increase of egg phenotypes variation perception in a cuckoo host.     

The impact on tropospheric ozone formation on the implementation of a program for mobile emissions control: a case study in São Paulo,Brazil

The main sources of reactive hydrocarbons (RHC) and nitrogen oxides (NO_x), ozone precursors, in the Metropolitan Area of São Paulo (MASP) in the southeast of Brazil are emissions from vehicles fleets. Ambient surface ozone and particulate matter concentrations are air quality problem in the MASP. This study examined the impact that implementing a control program for mobile emissions has on ozone concentrations, An episode of high surface ozone concentrations occurring in the MASP during the March 13–15, 2000 period was used as a case study that was modeled for photochemical oxidants using the California Institute of Technology/Carnegie Mellon University three-dimensional photochemical model. Different scenarios were analyzed in relationship to the implementation of the Programa Nacional de Controle de Poluição por Veículos Automotores (PROCONVE, National Program to Control Motor Vehicle Pollution). Scenario 1 assumed that all vehicles were operating within PROCONVE guidelines. Scenarios 2 and 3 considered hypothetical situations in which the PROCONVE was not implemented. Scenario 2 set the premise that vehicles were using pre-1989 technology, whereas scenario 3 allowed for technological advances. A base case scenario, in which the official emission inventory for the year 2000 was employed, was also analyzed. The CIT model results show agreement with most measurements collected during 13–15 March 2000 modeling episode. Mean normalized bias for ozone, CO, RHC and NO _x are approximately 9.0, 6.0, ?8.3, 13.0%, respectively. Tropospheric ozone concentrations predicted for scenario 2 were higher than those predicted for scenarios 1, 3 and base case. This study makes a significant contribution to the evaluation of air quality improvement and provides data for use in evaluating the economic costs of implementing a program of motor vehicle pollution control aimed at protecting human health.