Chitosan Functionalization with Amino Acids Yields to Higher Copper Ions Adsorption Capacity

Chitosan (Chi) beads were conjugated with three different amino acids [namely, glutamic acid (GLU), methionine (MET), and taurine (TAU)] aiming to increase the divalent copper ions uptake in aqueous media. Scanning Electron Microscopy evidenced the development of a large porous structure after amino acid functionalization, associated with the increase in a number of amino groups in the polymer backbone. X-Ray Photoelectron Spectroscopy and Fourier-Transform Infrared Spectra analyses were also employed to assess the conjugation of these three different amino acids in chitosan backbone. Adsorption experiments were conducted in a batch process, at 298 K, and kinetic data indicated a slightly better fitting for the pseudo-first-order model when compared to pseudo-second order. Intraparticle diffusion model suggested a three-step mechanism for Cu(II) adsorption kinetics, limited by the third step, the intraparticle diffusion. The isotherm data fitting to the traditional Langmuir and Freundlich models indicated a better fit for the former case. The amino acid conjugation resulted in the increase of the maximum adsorption capacity for Cu(II) from 1.30 mmol g^?1 prior to amino acid conjugation to values as high as 2.31 mmol g^?1, 2.40 mmol g^?1 and 2.68 mmol g^?1 for Chi–TAU, Chi–GLU, and Chi–MET, respectively. These results are attributed to the introduction of additional amino groups and new carboxylate and amino acid residues into the chitosan backbone, which might also be explored for amino acid demanding applications.     

Schizencephaly: Prenatal diagnosis by computed sonography and magnetic resonance imaging

Magnetic resonance (MR) imaging was performed at 29 weeks of pregnancy after ultrasonographic detection of an abnormal cleft in the fetal brain. Fetal neuromuscular blockade was induced by pancuronium bromide injected into the umbilical vein under continuous ultrasound (US) guidance. MR images supported the echotomographic diagnosis of schizencephaly improving the visualization of symmetrical broad clefts connecting the lateral ventricles with the subarachnoid space. Schizencephaly was finally confirmed by neonatal US, computed tomography, and MR.     

Trace gases and particulate matter emissions from wildfires and agricultural burning in Northeastern Mexico during the 2000 fire season

An inventory of air pollutants emitted from forest and agricultural fires in Northeastern Mexico for the period of January to August of 2000 is presented. The emissions estimates were calculated using an emissions factor methodology. The inventory accounts for the emission of carbon monoxide (CO), methane, nonmethane hydrocarbons, ammonia, nitrogen oxides, and particulate matter (PM). Particulate matter emissions include estimates for fine PM and coarse PM. A total of 2479 wildfires were identified in the domain for the period of interest, which represented approximately 810,000 acres burned and 621,130 short tons emitted (81% being CO). The main source of information used to locate and estimate the extent of the fires came from satellite imagery. A geographic information system was used to determine the type of vegetation burned by each fire. More than 54% of the total area burned during the period of study was land on the State of Tamaulipas. However, >58% of the estimated emissions came from the State of Coahuila. This was because of the mix of vegetation types burned in each state. With respect to the temporal distribution, 76.9% of the fires occurred during the months of April and May consuming almost 78% of the total area burned during the period of study. Analysis of wind forward trajectories of air masses passing through the burned areas and 850-mb wind reanalyses indicate possible transboundary transport of the emissions from Mexico to the United States during the occurrence of the major wildfires identified.     

The Role of a Salt Marsh Plant on Trace Metal Bioavailability in Sediments. Estimation By Different Chemical Approaches * (7 pp)

Goal, Scope and Background The presence or absence of vegetation can condition sediment characteristics. The main aim of this work was to investigate the influence of the sea rush Juncus maritimus on metal (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) availability to organisms living on or in estuarine sediments, from Douro River (NW Portugal), by comparing the characteristics and chemical behaviour of rhizosediments (collected within the plant assemblage) and those of sediment (collected around the plant). In order to evaluate whether and how sediment characteristics condition the role of plants on metal availability, sandy and muddy sediments colonised by J. maritimus were studied in parallel. Methods Metal availability was estimated by enzymatic digestion with pepsin (ED), which may provide an estimate of metal availability to organisms living at estuarine sediments. Nevertheless, since no consensus exists yet on the most suitable methodologies to estimate metal bioavailability in sediments, two more conventional approaches, BCR sequential extraction (SE) and AVS/SEM model, were also used, in parallel, and the information these approaches provided was compared with that provided by ED. Total-recoverable metal contents were determined by atomic absorption spectrophotometry after sediment digestion using a high-pressure microwave system. Results and Discussion Plants could concentrate metals around its roots and rhizomes. In addition, they were capable of oxidizing (release of oxygen by the roots) the anaerobic medium surrounding their roots in muddy sediment (reducing AVS). As sulphide oxidation renders metals (Cd, Cu, Ni, Pb and Zn) into more soluble forms, according to the AVS/SEM model, metals from muddy sites would be more available in rhizosediment than in sediment. The SE approach led to a similar conclusion. Nevertheless, the results provided by ED pointed at opposite conclusion, particularly for Cd and Zn, indicating less availability at rhizosediments than in the surrounding sediment. ED results were interpreted as a consequence of an enrichment of the rhizosediment in organic ligands exuded by the roots or liberated by dead plants. The effect of complexation of metals by organic compounds, which ED could not decompose/dissolve, seemed to overcome that caused by sediment oxidation. In general, a comparison of the information about metal availability by ED, SE, AVS/SEM, showed that it did not always match and in few cases it was even contradictory. Conclusion and Outlook Therefore, a thorough evaluation of the metal availability in sediments requires a combination of different chemical approaches, so as to take into consideration differences in ways of organism exposure (interstitial water and/or ingestion of sediment particles). - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Fungitoxicity of lyophilized and spray-dried garlic extracts

Among the compounds discussed for anti-microbial and anti-fungal use allicin (allylthiosulfinate, diallyl disulfide-S-monoxide), an active ingredient of garlic, has attracted considerable attention. The objective of this study is to determine the antifungal activity of a local garlic ecotype (Voghiera) extracts against different pathogens. Primary screening was carried out by the agar plates technique using ethanol garlic extract at four final concentrations against the following organisms: Alternaria alternata, Aspergillus spp., Colletotrichum acutatum, Didymella bryoniae, Fusarium culmorum, Fusarium avenaceum, Fusarium gramineareum, Gliocladium roseum 47, Pythium splendens, Rhizoctonia solani, Sclerotium rolfsii, Stemphylium vesicarium, Trichoderma longibranchiatum, and Botrytis cinerea. Secondary screening was carried out using a lyophilized and a spray-dried preparation at different concentrations against the organisms selected for the high inhibition garlic effect in the primary screening and compared with the commercial fungicides mancozeb and iprodione. The best results were observed for the spray-dried garlic compound that showed a good fungicidal activity at the concentration of 1.5 g/10 mL while lyophilized garlic at the same concentration exhibithed less inhibition activity against the four fungi analyzed in the second screening.     

Pregnancy patterns of pantropical spotted dolphins (Stenella attenuata) in the eastern tropical Pacific determined from hormonal analysis of blubber biopsies and correlations with the purse-seine tuna fishery

The northeastern offshore population of the pantropical spotted dolphin (Stenella attenuata) in the eastern tropical Pacific remains listed as depleted under the Marine Mammal Protection Act, and recent estimates of abundance show that recovery has been slow. One hypothesis for the slow recovery is that continued chase and encirclement by the tuna fishery negatively affects reproduction. Insufficient life-history sampling in this region over the last two decades makes traditional estimates of reproductive rates impossible. Here, we examine the current reproductive patterns of these dolphins by measuring blubber progesterone (BP) concentrations in biopsy samples to assess pregnancy state. BP was quantified in 212 biopsies from female offshore spotted dolphins sampled between 1998 and 2003 in the northeastern tropical Pacific, and we found that 11.5 % of the biopsied females (mature and immature) were pregnant. The relationship between pregnancy and fishery exposure was analyzed, and we found that pregnant females were exposed to significantly less fishery activity than non-pregnant ones (p = 0.022), suggesting that the fishery may have an inhibitive effect on pregnancy. Spatial analysis indicated that pregnancy was more aggregated than random (p < 0.05) at a scale up to 180-nmi, with the highest proportion pregnant in the mouth of the Gulf of California, an area with relatively low reported fishery activity.     

Effects of Cutrine-Plus® algaecide and predators on wood frog (Lithobates sylvaticus) tadpole survival and growth

Copper contamination is increasing in many aquatic ecosystems. One mode by which copper can be introduced into aquatic ecosystems is as an algaecide, such as Cutrine-Plus®. Using a mesocosm experiment, we examined the effects of Cutrine-Plus® on wood frog (Lithobates sylvaticus) tadpoles. In addition, we examined how the presence of a nonnative predator the Western mosquitofish (Gambusia affinis) may interact with exposure to Cutrine-Plus®. Exposure to our low and high Cutrine-Plus® treatments had a strong negative effect on the wood frog tadpoles, and survivorship was greatly decreased in the low treatment, and no tadpoles survived in the high treatment. Additionally, the tadpoles that survived the low treatment were significantly smaller than those in the control treatment. Mosquitofish had no effect on the survivorship or growth of wood frog tadpoles, and mosquitofish presence did not have a significant interaction with the Cutrine-Plus® treatments. Cutrine-Plus® clearly had a negative effect on wood frog tadpoles at the concentrations used in our experiment, which were at and below the label-recommended dosages, suggesting that the use of Cutrine-Plus® in natural ponds may have negative consequences for wood frog populations and possibly other amphibians.     

Metal levels in sediments from the Minho estuary salt marsh: a metal clean area?

Total-recoverable metals (Al, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in sediments from Minho estuary salt marsh were determined to evaluate possible increase in anthropogenic contamination by metals and to evaluate the possibility of this area to be considered a pristine area in terms of metals, which can be used as a reference site for other metal-contaminated national and international estuaries/salt marshes. This study revealed that the spatial distribution of metals in the salt marsh sediments was not homogeneous and that two sampling sites (sites 5 and 7) had indications of anthropogenic contamination. However, metal levels in these salt marsh sediments were lower than those observed in the wetlands of the main Portuguese estuaries. Comparison with Portuguese and international reference values used in the evaluation of the ecological quality of sediments, indicated that the sediments can be classified as “clean sediment” and that metal levels were lower or similar (only for Cu and Ni) to the values of ERL, which are the values that define the concentrations ranges that are rarely associated to adverse biologic effects in organisms. In addition, metal levels in the sediments were in chemical forms that were not easily available to organisms, indicating that these sediments probably will not have negative influences in the organisms living in the salt marsh, although no life-form ecological safety tests have been carried out. Therefore, the Minho estuary salt marsh area can probably be considered a pristine area in terms of metals and can be used as a reference for other metal-contaminated estuaries/salt marshes.     

Trace Gases and Particulate Matter Emissions from Wildfires and Agricultural Burning in Northeastern Mexico during the 2000 Fire Season

Abstract

An inventory of air pollutants emitted from forest and agricultural fires in Northeastern Mexico for the period of January to August of 2000 is presented. The emissions estimates were calculated using an emissions factor methodology. The inventory accounts for the emission of carbon monoxide (CO), methane, nonmethane hydrocarbons, ammonia, nitrogen oxides, and particulate matter (PM). Particulate matter emissions include estimates for fine PM and coarse PM. A total of 2479 wildfires were identified in the domain for the period of interest, which represented ~810,000 acres burned and 621,130 short tons emitted (81% being CO). The main source of information used to locate and estimate the extent of the fires came from satellite imagery. A geographic information system was used to determine the type of vegetation burned by each fire. More than 54% of the total area burned during the period of study was land on the State of Tamaulipas. However, >58% of the estimated emissions came from the State of Coahuila. This was because of the mix of vegetation types burned in each state. With respect to the temporal distribution, 76.9% of the fires occurred during the months of April and May consuming almost 78% of the total area burned during the period of study. Analysis of wind forward trajectories of air masses passing through the burned areas and 850-mb wind reanalyses indicate possible transboundary transport of the emissions from Mexico to the United States during the occurrence of the major wildfires identified.     

Establishing the redox potential of Tibouchina pulchra (Cham.) Cogn., a native tree species from the Atlantic Rain Forest,in the vicinity of an oil refinery in SE Brazil

The present study aimed to establish the seasonal variations in the redox potential ranges of young Tibouchina pulchra plants growing in the Cubatão region (SE Brazil) under varying levels of oxidative stress caused by air pollutants. The plants were exposed to filtered air (FA) and non-filtered air (NFA) in open-top chambers installed next to an oil refinery in Cubatão during six exposure periods of 90 days each, which included the winter and summer seasons. After exposure, several analyses were performed, including the foliar concentrations of ascorbic acid and glutathione in its reduced (AsA and GSH), total (totAA and totG) and oxidized forms (DHA and GSSG); their ratios (AsA/totAA and GSH/totG); the enzymatic activities of superoxide dismutase (SOD), ascorbate peroxidase (APX), catalase (CAT) and glutathione reductase (GR); and the content of malondialdehyde (MDA). The range of antioxidant responses in T. pulchra plants varied seasonally and was stimulated by high or low air pollutant concentrations and/or air temperatures. Glutathione and APX were primarily responsible for increasing plant tolerance to oxidative stress originating from air pollution in the region. The high or low air temperatures mainly affected enzymatic activity. The content of MDA increased in response to increasing ozone concentration, thus indicating that the pro-oxidant/antioxidant balance may not have been reached.