Analytical pyrolysis to study microplastics and other polymers in the environment

Synthetic polymers constitute a wide class of materials which has enhanced the quality of human life, providing comforts and innovations. Anyway, the increasing production and the incorrect waste management, are leading to the occurrence of polymers in the environment, generating concern. To understand the extent of this issue, analytical investigation holds an essential position. Standardised methods have not established yet, and additional studies are required to improve the present knowledge. The main aim of this thesis was to provide comprehensive information about the potential of pyrolysis coupled with gas-chromatography and mass spectrometry (Py-GC-MS) for polymers investigation, from their characterisation to their identification and quantification in complex matrices. Water-soluble (poly(dimethylsiloxanes), PDMS bearing poly(ethylene glycol), PEG, side chains) and water-insoluble polymers (microplastics, MPs, and bioplastics) were studied. The different studies revealed the possibility to identify heterogeneous classes of polymers, fingerprinting the presence of PDMS copolymers and distinguishing chemically different polyurethanes (PURs). The occurrence of secondary reactions in pyrolysis of polymer mixtures was observed as possible drawback. Pyrolysis products indicative of secondary reactions and their reaction mechanisms were identified. Py-GC-MS also revealed its fundamental role for the identification of polymers composing commercial bioplastics items based. The results aided to identify chemicals that have the potential to migrate in sea waters. Investigations of environmental samples demonstrated the capability of Py-GC-MS to provide reliable, reproducible and comparable results about polymers in complex matrices (PEG-PDMS in sewage sludges and PURs and other MPs in road dusts and spider webs). Criticisms were especially found in quantitation, such as the retrieval reference materials, the construction of reliable calibration protocols and the occurrence of bias due to interferences between pyrolysis products. This thesis pursues the greater purpose to develop harmonised and standardised methods for environmental investigations of polymers, that is fundamental to assess the real state of the environment.

Access to climate justice: the main procedural hurdles, and possible solutions, within the italian legal framework and the IBA Model Statute

The thesis deals with standing and justiciability in climate litigation against governments and the private sector. The first part addresses the impacts of climate change on human rights, the major developments in international climate law, and the historical reasons for climate litigation. The second part analyses several cases, divided into categories. It then draws to a comparative conclusion with regard to each category. The third part deals with the Italian legal tradition on standing and justiciability – starting from the historical roots of such rules. The fourth part introduces the ‘Model Statute’ drafted by the International Bar Association, arguing that the 'ratio legis' of this proposal could be implemented in Italy or the EU. The thesis develops arguments, based on the existing legal framework, to help plaintiffs establish standing and justiciability in proceedings pending before Italian courts. It further proposes the idea that 'citizen suits' are consistent with the Italian and EU legal tradition and that the EU could rely on citizen suits to privately enforce its climate law and policies under the ‘European Green Deal.’

Three-dimensional solution structure of alpha-conotoxin MII by NMR spectroscopy: Effects of solution environment on helicity

alpha-Conotoxin MII, a 16-residue polypeptide from the venom of the piscivorous cone snail Conus magus, is a potent and highly specific blocker of mammalian neuronal nicotinic acetylcholine receptors composed of alpha 3 beta 2 subunits. The role of this receptor type in the modulation of neurotransmitter release and its relevance to the problems of addiction and psychosis emphasize the importance of a structural understanding of the mode of interaction of MII with the alpha 3 beta 2 interface. Here we describe the three-dimensional solution structure of MIT determined using 2D H-1 NMR spectroscopy. Structural restraints consisting of 376 interproton distances inferred from NOEs and 12 dihedral restraints derived from spin-spin coupling constants were used as input for simulated annealing calculations and energy minimization in the program X-PLOR. The final set of 20 structures is exceptionally well-defined with mean pairwise rms differences over the whole molecule of 0.07 Angstrom for the backbone atoms and 0.34 Angstrom for all heavy atoms. MII adopts a compact structure incorporating a central segment of alpha-helix and beta-turns at the N- and C-termini. The molecule is stabilized by two disulfide bonds, which provide cross-links between the N-terminus and both the middle and C-terminus of the structure. The susceptibility of the structure to conformational change was examined using several different solvent conditions. While the global fold of MII remains the same, the structure is stabilized in a more hydrophobic environment provided by the addition of acetonitrile or trifluoroethanol to the aqueous solution. The distribution of amino acid side chains in MII creates distinct hydrophobic and polar patches on its surface that may be important for the specific interaction with the alpha 3 beta 2 neuronal nAChR. A comparison of the structure of MII with other neuronal-specific alpha-conotoxins provides insights into their mode of interaction with these receptors.

Effect of radiation environment on radiation use efficiency and growth of sunflower

The level of incident radiation and the proportion of radiation that is diffuse affects radiation use efficiency (RUE) in crops, However, the degree of this effect, and its importance to growth and yield of sunflower (Helianthus annuus L.) have not been established. A field experiment was conducted to investigate the effects of radiation environment on RUE, growth, and yield of sunflower. A fully irrigated crop was sown on an alluvial-prairie soil (Fluventic Haplustoll) and was exposed to three distinct radiation environments. In two treatments, the level of incident radiation was reduced by 14 and 20% by suspending tao different types of polyethylene plastic films well above the crop. In addition to the reductions in incident radiation, the proportion of radiation that was diffuse was increased by about 14% in these treatments. Lower incident radiation and increased proportion of diffuse radiation had no effect on total biomass, phenology, leaf area, and the canopy light extinction coefficient (k = 0.89). However, yield was reduced in shaded treatments due to smaller grain size and lower harvest index. Although crop RUE measured over the entire crop cycle (1.25 g/MJ) did not differ significantly among treatments, there was a trend where RUE compensated for less intercepted incident radiation. Theoretical derivations of the response of RUE to different levels of incident radiation supported this finding. Shaded sunflower crops have the ability to produce biomass similar to unshaded crops by increasing RUE, but have lower harvest indices.

Timing-dependent protection of hypertonic saline solution administration in experimental liver ischemia/reperfusion injury

Background. Diving liver ischemia, the decrease in mitochondrial energy causes cellular damage that is aggravated after reperfusion. This injury can trigger a systemic inflammatory syndrome, also producing remote organ damage. Several substances have been employed to decrease this inflammatory response during liver transplantation, liver resections, and hypovolemic shock. The aim of this study was to evaluate the effects of hypertonic saline solution and the best timing of administration to prevent organ injury during experimental liver ischemia/reperfusion. Methods. Rats underwent 1 hr of warm liver ischemia followed by reperfusion. Eighty-four rats Were allocated into 6 groups: sham group, control of ischemia group) (C), pre-ischemia treated NaCl 0.9% (ISS) and NaCl 7.5% (HTS) groups, pre-repefusion ISS, and HTS groups. Blood and tissue samples were collected 4 hr after reperfusion. Results. HTS showed beneficial effects in prevention of live ischemia/reperfusion injury. HTS groups developed increases in AST and ALT levels that were significantly less than ISS groups; however, the HTS pre-reperfusion group showed levels significantly less than the HTS pre-ischemia group. No differences in IL-6 and IL-10 levels, were observed. A significant decrease in mitochondrial dysfunction as well as hepatic edema was observed in the HTS pre-reperfusion group. Pulmonary vascular permeability Was significantly less in the pre-reperfusion HTS group compared to the ISS group. No differences in myeloperoxidase activity were observed. The liver histologic score was significantly less in the pre-reperfusion HTS group compared to the pre-ischemia I-ITS group. Conclusion. HTS ameliorated local and systemic injuries in experimental liver ischemia/reperfusion. Infusion of HTS in the pre-reperfusion period may be an important adjunct to accomplish the best results. (Surgery 2010;147:415-23.)

Coupling 3D visualisation to qualitative assessment of built environment designs

Geographical information systems (GIS) coupled to 3D visualisation technology is an emerging tool for urban planning and landscape design applications. The utility of 3D GIS for realistically visualising the built environment and proposed development scenarios is much advocated in the literature. Planners assess the merits of proposed changes using visual impact assessment (VIA). We have used Arcview GIS and visualisation software: called PolyTRIM from the University of Toronto, Centre for Landscape Research (CLR) to create a 3D scene for the entrance to a University campus. The paper investigates the thesis that to facilitate VIA in planning and design requires not only visualisation, but also a structured evaluation technique (Delphi) to arbitrate the decision-making process. (C) 2001 Elsevier Science B.V. All rights reserved.

Protection of mice from group A streptococcal infection by intranasal immunisation with a peptide vaccine that contains a conserved M protein B cell epitope and lacks a T cell autoepitope

Infection with group A streptococci (GAS) can lead to rheumatic fever (RF) and rheumatic heart disease (RHD) which are a major health concern particularly in indigenous populations worldwide, and especially in Australian Aboriginals. A primary route of GAS infection is via the upper respiratory tract, and therefore, a major goal of research is the development of a mucosal-based GAS vaccine, The majority of the research to date has focused on the GAS M protein since immunity to GAS is mediated by M protein type-specific opsonic antibodies. There are two major impediments to the development of a vaccine-the variability in M proteins and the potential for the induction of an autoimmune response. To develop a safe and broad-based vaccine, we have therefore focused on the GAS M protein conserved C-region, and have identified peptides, J8 and the closely related J8 peptide (J14), which may be important in protective immunity to GAS infection. Using a mucosal animal model system, our data have shown a high degree of throat GAS colonisation in B10.BR mice 24 h following intranasal immunisation with the mucosal adjuvant, cholera toxin B subunit (CTB), and/or diptheria toxoid (dT) carrier, or PBS alone, and challenge with the M1 GAS strain. However, GAS colonisation of the throat was significantly reduced following intranasal immunisation of mice with the vaccine candidate J8 conjugated to dT or J14-dT when administered with CTB. Moreover, J8-dT/CTB and J14-dT/CTB-immunised mice had a significantly higher survival when compared to CTB and PBS-immunised control mice. These data indicate that immunity to GAS infection can be evoked by intranasal immunisation with a GAS M protein C-region peptide vaccine that contains a protective B cell epitope and lacks a T cell autoepitope. (C) 2002 Published by Elsevier Science Ltd.

A generic model for integration of Quality, Environment and Safety Management Systems

Purpose – The purpose of this paper is to propose a generic model of Integrated Management System of Quality, Environment and Safety (IMS-QES) that can be adapted and progressively to assimilate various Management Systems, of which highlights: ISO 9001 for Quality; ISO 14001 for Environment; OHSAS 18001 for Occupational Health and Safety. Design/methodology/approach – The model was designed in the real environment of a Portuguese Organization and 160 employees were surveyed. The rate response was equal to 86 percent. The conceived model was implemented in a first phase for the integration of Quality, Environment and Safety Management Systems. Findings – Among the main findings of the survey the paper highlights: the elimination of conflicts between individual systems with resources optimization; creation of added value to the business by eliminating several types of wastes; the integrated management of sustainability components in a global market; the improvement of partnerships with suppliers of goods and services; reducing the number of internal and external audits. Originality/value – This case study is one of the first Portuguese empirical researches about IMS-QES and the paper believes that it can be useful in the creation of a Portuguese guideline for integration, namely the Quality Management Systems; Environmental Management Systems and Occupational Health and Safety Management Systems among others.