Novel Glycopolymers Based on d-Mannose and Methacrylates: Synthesis, Thermal Stability and Biodegradability Testing

This paper presents the synthesis, thermal stability and biodegradability of new d-mannose glycopolymers. These glycopolymers have been obtained by free radical bulk copolymerization of d-mannose based glycomonomer, 1-O-(2′-hydroxy-3′-methacryloyloxypropyl)-2,3:5,6-di-O-isopropylidene-d-mannofuranose (Mm), and respectively d-mannose derived oligomer (Mo) with methyl methacrylate and respectively 2-hydroxypropyl methacrylate. The chemical structures of Mm and Mo have been confirmed via FTIR, ¹H-NMR and HPLC–MS spectroscopy. The copolymerization process has been investigated using differential scanning calorimetry, which allowed calculating the activation energies by applying Kissinger–Akahira–Sunose method. The glycopolymers are thermally stable, fact assessed by TG analysis; their glass transition temperature exceeds 50 °C, so they are part of the glassy class of polymers. The biodegradability of these glycopolymers has been investigated in vitro, using pure cultures of Zymomonas mobilis and Trichoderma reesei. The glycopolymers lose up to 55 % weight in just 14 days of incubation as their surface and composition is altered by colonies of microorganisms that grow on/into them, fact demonstrated using SEM/EDX.     

A model for prediction of product distributions for the reactions of phenol derivatives with hydroxyl radicals

In this study, with the intention of estimating the photocatalytic or photodegradation rates and finding certain predictors to be used for the determination of the most probable reaction path and the primary intermediate, the reactions of (*)OH radicals with 11 phenol derivatives including benzene were modeled. For 43 possible reaction routes, calculations of the geometric parameters, the electronic and thermodynamic properties of the reactants, the product radicals and the transition state complexes were performed with the semiempirical PM3 and DFT/B3LYP/6-31G(*) methods. The solvation effects were computed using COSMO as the solvation model. Based on the results of quantum mechanical calculations, the rate constants, the branching ratios and the product distributions of all the possible reaction paths were calculated by means of the transition state theory. Three predictors were determined for the prediction of the most probable transition state and the reaction path. The differences in the reaction rates were explained in terms of the presence of hydrogen bonds in the transition state complexes and the entropy effects. Finally the results obtained were compared with the available experimental data in order to assess the reliability of the proposed model.     

Comparative environmental impacts of glyphosate and conventional herbicides when used with glyphosate-tolerant and non-tolerant crops

The introduction of glyphosate-tolerant (GT) crops is expected to mitigate the environmental contamination by herbicides because glyphosate is less persistent and toxic than the herbicides used on non-GT crops. Here, we compared the environmental balances of herbicide applications for both crop types in three French field trials. The dynamic of herbicides and their metabolites in soil, groundwater and air was simulated with PRZM model and compared to field measurements. The associated impacts were aggregated with toxicity potentials calculated with the fate and exposure model USES for several environmental endpoints. The impacts of GT systems were lower than those of non-GT systems, but the accumulation in soils of one glyphosate metabolite (aminomethylphosphonic acid) questions the sustainability of GT systems. The magnitude of the impacts depends on the rates and frequency of glyphosate application being highest for GT maize monoculture and lowest for combination of GT oilseed rape and non-GT sugarbeet crops.     

Gaseous nitrogen emissions and forage nitrogen uptake on soils fertilized with raw and treated swine manure

Treatments to reduce solids content in liquid manure have been developed, but little information is available on gaseous N emissions and plant N uptake after application of treated liquid swine manure (LSM). We measured crop yield, N uptake, and NH3 and N2O losses after the application of mineral fertilizer (NH4 NO3), raw LSM, and LSM that was decanted, filtered, anaerobically digested, or chemically flocculated. The experiment was conducted from 2001 to 2003 on a loam and a sandy loam cropped to timothy (Phleum pratense L.) with annual applications equivalent to 80 kg N ha(-1) in spring and 60 kg N ha(-1) after the first harvest. Raw LSM resulted in NH3 emissions three to six times larger (P < 0.05) than mineral fertilizer. The LSM treatments reduced NH3 emissions by an average of 25% compared with raw LSM (P < 0.05). The N2O emissions tended to be higher with raw LSM than with mineral fertilizer. The LSM treatments had little effect on N2O emissions, except for anaerobic digestion, which reduced emissions by >50% compared with raw LSM (P < 0.05). Forage yield with raw LSM was >90% of that with mineral fertilizer. The LSM treatments tended to increase forage yield and N uptake relative to raw LSM. We conclude that treated or untreated LSM offers an alternative to mineral fertilizers for forage grass production but care must be taken to minimize NH3 volatilization. Removing solids from LSM by mechanical, chemical, and biological means reduced NH3 losses from LSM applied to perennial grass.     

Extinction in a hyperdiverse endemic Hawaiian land snail family and implications for the underestimation of invertebrate extinction

The International Union for Conservation of Nature (IUCN) Red List includes 832 species listed as extinct since 1600, a minuscule fraction of total biodiversity. This extinction rate is of the same order of magnitude as the background rate and has been used to downplay the biodiversity crisis. Invertebrates comprise 99% of biodiversity, yet the status of a negligible number has been assessed. We assessed extinction in the Hawaiian land snail family Amastridae (325 species, IUCN lists 33 as extinct). We did not use the stringent IUCN criteria, by which most invertebrates would be considered data deficient, but a more realistic approach comparing historical collections with modern surveys and expert knowledge. Of the 325 Amastridae species, 43 were originally described as fossil or subfossil and were assumed to be extinct. Of the remaining 282, we evaluated 88 as extinct and 15 as extant and determined that 179 species had insufficient evidence of extinction (though most are probably extinct). Results of statistical assessment of extinction probabilities were consistent with our expert evaluations of levels of extinction. Modeling various extinction scenarios yielded extinction rates of 0.4‐14.0% of the amastrid fauna per decade. The true rate of amastrid extinction has not been constant; generally, it has increased over time. We estimated a realistic average extinction rate as approximately 5%/decade since the first half of the nineteenth century. In general, oceanic island biotas are especially susceptible to extinction and global rate generalizations do not reflect this. Our approach could be used for other invertebrates, especially those with restricted ranges (e.g., islands), and such an approach may be the only way to evaluate invertebrates rapidly enough to keep up with ongoing extinction.     

Post-ejection nest-desertion of common cuckoo hosts: a second defense mechanism or avoiding reduced reproductive success?

Hosts of the common cuckoo (Cuculus canorus), an avian brood parasite, develop antiparasite defense mechanisms to increase their reproductive success. Ejection of the parasite egg and desertion of the parasitized nest are the most typical adaptations in response to brood parasitism, but nest desertion may also occur in response to partial clutch reduction, independently from parasitism. Some great reed warblers (Acrocephalus arundinaceus) showed both mechanisms in the same incidence of cuckoo parasitism: in 18% of successful ejections of the parasite eggs, they deserted their nests. We studied if such cases of post-ejection nest-desertion are caused by brood parasitism or reduced clutch value. We experimentally parasitized clutches consisting of five or three host eggs with two painted conspecific eggs to mimic parasitic eggs, as multiple parasitism is frequent in the area. Although hosts ejected these parasitic eggs in both clutch categories (100% and 67% for the larger and smaller inital clutch sizes, respectively), we found that after manipulation, post-ejection nest-desertion frequently occurred at small (3-egg) clutches (40%), but rarely at large (5-egg) clutches (17%). The same phenomenon also occurred when unparasitized 3-egg clutches were reduced by two eggs, but not when 5-egg clutches were reduced in the same way. A logistic regression model revealed that only initial clutch size affected nest desertion of parasitized nests in our experiments. Therefore, we conclude that post-ejection nest-desertion is not a second antiparasite mechanism, which might serve as a redundant antiparasite defense, but a reaction to typically small and further decreased clutch size.     

Multi-geochemical background comparison and the identification of the best normalizer for the estimation of PTE contamination in agricultural soil

Environmental Geochemistry and Health - Identifying a suitable geochemical background level (GBL) and an appropriate normalizer is imperative for ensuring soil quality, health, and security. The...     

Modification of cyclodextrin and use in environmental applications

Environmental Science and Pollution Research - Water pollution, which has become a global problem in parallel with environmental pollution, is a problem that needs to be solved urgently,...     

Changing the Course of Rivers in an Asian City: Linking Landscapes to Human Benefits through Iterative Modeling and Design

Concerns over water scarcity, climate change, and environmental health risks have prompted some Asian cities to invest in river rehabilitation, but deciding on the end goals of rehabilitation is a complex undertaking. We propose a multidisciplinary framework linking riparian landscape change to human well‐being, providing information relevant to decision makers, in a format that facilitates stakeholder involvement. We illustrate this through a case study of the densely settled, environmentally degraded, and flood prone Ciliwung River flowing through metropolitan Jakarta, Indonesia. Our methodology attempts to respond to this complexity through an iterative approach, strongly based on conceptualization and mathematical modeling. Nested hydrologic, hydrodynamic, and water quality models provide outputs at catchment‐, corridor‐, and localized site‐scales. Advanced 3‐D landscape modeling is used for procedural design and precise visualization of proposed changes and their impacts, as predicted by the mathematical models. Finally, participatory planning and design methods allow us to obtain critical stakeholder feedback in shaping a socially acceptable approach. Our framework aims at demonstrating that a change in paradigm in river rehabilitation is possible, and providing future scenarios that balance concerns over flooding, water quality, and ecology, with the realities of a rapidly growing megacity.     

Ecological tracers and at-sea observations document the foraging ecology of southern long-finned pilot whales (<Emphasis Type="Italic">Globicephala melas edwardii</Emphasis>) in Kerguelen waters

The food and feeding ecology of the poorly known southern long-finned pilot whale (Globicephala melas edwardii) was investigated using ecological tracers (muscle and skin δ¹³C and δ¹⁵N, and total mercury, Hg) on individuals from two mass strandings together with at-sea observations of live animals in Kerguelen waters, southern Indian Ocean. Sightings of cetaceans from longliners over 9 years (2003–2012) emphasized the regular occurrence of pilot whales in slope waters surrounding the archipelago. Tissue δ¹³C values (a proxy of consumer foraging habitat) suggest that pilot whales fed in slope waters and in oceanic subantarctic waters over the last months preceding stranding. Tissue δ¹⁵N values and Hg concentration (dietary proxies) indicate a high trophic position (~4.7) for the pilot whales, likely corresponding to a mixed diet of fish and squid (not crustaceans) of undetermined species. Both skin and muscle Hg concentrations were positively and linearly correlated to individual size with no concomitant δ¹⁵N changes, which can be interpreted as a progressive Hg accumulation in tissues of individuals throughout life with no parallel dietary shift. Skin and muscle Hg concentrations were linearly and positively related; hence, Hg skin could be used as a proxy of Hg concentration in muscle (a main Hg reservoir of the body). Kerguelen southern long-finned pilot whales were less Hg contaminated than most pilot whale populations studied so far, thus suggesting that they are not at a high risk to Hg-induced damages in the remote islands of the Southern Ocean.