Thermogravimetric pyrolysis of waste polyethylene-terephthalate and polystyrene: A critical assessment of kinetics modelling

Pyrolysis is considered as possible technique to thermally convert waste plastics into chemicals and energy. Literature on experimental findings is extensive, although experiments are mostly performed in a dynamic heating mode, using thermogravimetric analysis (TGA) and at low values of the heating rate (mostly below 30 K/min). The present research differs from literature through the application of far higher heating rates, up to 120 K/min. The use of these dynamic results to define the reaction kinetics necessitates the selection of an appropriate reaction mechanism, and 21 models have been proposed in literature considering the rate limiting step being diffusion, nucleation or the reaction itself.The current research studied the cracking of PET and PS by TGA at different heating rates (temperature ramps). Results were used to check the validity of the proposed mechanisms. Several conclusions are drawn: (i) to obtain fair results, the heating ramp should exceed a minimum value, calculated at 30 K/min for PET and 80 K/min for PS; (ii) application of the majority of the models to experimental findings demonstrated that they do not meet fundamental kinetic considerations and are questionable in their use; and (iii) simple models, with reaction order 1 or 2, provide similar results of the reaction activation energy.A further comparison with literature data for dynamic and isothermal experiments confirms the validity of these selected models. Since TGA results are obtained on a limited amount of sample, with results being a strong function of the applied heating rate, the authors believe that isothermal experiments, preferably on a large scale both towards equipment and/or sample size, are to be preferred.     

Anaerobic transformation of four abundant organochlorine pesticide residues (B8-1413, B9-1679, oxychlordane,p,p‵-DDE) in extracts of Antarctic skua eggs by the isolated bacterium Sulfurospirillum multivorans

Residues of halogenated pollutants bioaccumulated in eggs of the south polar skua (Catharacta maccormicki) from the Antarctic were extracted, purified, and fractionated. The target fraction which contained the bulk of the chloropesticides was concentrated and incubated with cell suspensions of the isolated bacterium Sulfurospirillum multivorans (formerly Dehalospirillum multivorans). S. multivorans was previously identified as a good anoxic transformer of several halogenated compounds. The compounds of technical toxaphene 2-endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413, also known as P-26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679, also known as P-50) as well as 1,1-dichloro-2,2-bis(p-chlorophenyl)ethene (p,p′-DDE) and 1-exo,2-exo,4,5,6,7,8,8-octachloro-2,3-exo-epoxy-3a,4,7,7a-tetrahydro-4,7-methanoindene (oxychlordane) were present at a sufficiently high concentration and hence useful for studying the anaerobic transformation by the bacterium. When treated with S. multivorans, B8-1413 and B9-1679 were almost quantitatively transformed within 1 day. For B9-1679, the major metabolite was found to be 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane (B7-1001). Compared to the toxaphenes, transformation of oxychlordane and p,p′-DDE was significantly slower. Even after seven days, about 10% of the initial pool was detected in the extracts. 1-chloro-2,2-bis(p-chlorophenyl)ethene (p,p′-DDMU) was identified as a transformation product of p,p′-DDE. The four compounds in this study comprise some of the most persistent chloropesticide residues found in marine birds. In case there is sufficient transformation before they reach the top predators, the bioaccumulative potential can be significantly reduced.     

The roach (Rutilus rutilus) as a sentinel for assessing endocrine disruption.

Alterations in development and reproduction as a consequence of exposure to endocrine-disrupting chemicals (EDCs) have been demonstrated in many wildlife species. Animals living in, or closely associated with, the aquatic environment are particularly vulnerable to endocrine disruption because thousands of chemicals are actively disposed into rivers, estuaries and seas. Fish have thus been a focus in endocrine disruption studies, and some of the most comprehensive studies on the disruption of sexual development and function are on the roach (Rutilus rutilus). This paper provides a critical analysis of the roach as a sentinel for studies into endocrine disruption. The paper starts by describing what is known on the basic reproductive biology of the roach, information essential for interpreting chemical effect measures on sexual development and function. We then analyze where and how the roach has been applied to improve our understanding of the estrogenic nature of discharges from wastewater treatment works (WWTWs) and describe the phenomenon of feminized male roach in UK rivers. In this paper, the causation of these effects and issues of relative susceptibility and sensitivity of the roach to the effects of estrogenic EDCs are addressed. The paper then describes the ongoing work on the development of genetic and genomic resources for roach and analyses how these are being applied in studies to understand the mechanisms of disruption of sexual development. Finally, the paper addresses the biological significance of sexual disruption and intersex for the individual and discusses the possible implications for wild populations.     

Polymeric cracking of waste polyethylene terephthalate to chemicals and energy

Polyethylene terephthalate (PET) is a widely used thermoplastic. PET residues represent on average 7.6 wt% of the different polymer wastes in Europe. Pyrolysis of these wastes is attracting increasing interest, and PET is a potential candidate for this thermal process. The paper measures and discusses the kinetics of the pyrolysis reaction in terms of the reaction rate constants as determined by dynamic thermogravimetric analysis, with special emphasis on the required heating rate to obtain relevant results. The product yields and compositions are also determined. Gaseous products represent 16-18 wt%. The amounts of condensables and carbonaceous residue are a function of the operating mode, with slow pyrolysis producing up to 24 wt% of carbonaceous residue. Major condensable components are benzoic acid, monovinyl terephthalate, divinyl terephthalate, vinyl benzoate, and benzene. The present paper complements previous literature findings by (1) the study of the influence of the heating rate on the reaction kinetics in dynamic pyrolysis tests, (2) the isothermal investigation in a fluidized bed reactor to pyrolyze PET, and (3) the assessment of upgrading and recovery of the products. The paper concludes with a proposed reactor recommendation for PET pyrolysis, in either the bubbling or circulating fluidized bed operating mode.     

Leaf litter leachates have the potential to increase lifespan, body size, and offspring numbers in a clone of Moina macrocopa

Leaf litter processing is one major pathway of the global organic carbon cycle. During this process, a variety of small reactive organic compounds are released and transported to the aquatic environment, and may directly impact aquatic organisms as natural xenobiotics. We hypothesize that different forest stockings produce different leachate qualities, which in turn, stress the aquatic communities and, eventually, separate sensitive from tolerant species. Particularly, leachates from coniferous trees are suspected to have strongly adverse impacts on sensitive species. We exposed individuals of a clone of the model organism, Moina macrocopa, to comparable concentrations (approximately 2 mM) of litter leachates of Norway spruce, Picea abies, Colorado blue spruce, Picea pungens, black poplar, Populus nigra, and sessile oak, Quercus petraea. The animals were fed ad libitum. The following life trait variables were recorded: growth, lifespan, and lifetime offspring. To identify, whether or not exposure to litter leachates provokes an internal oxidative stress in the exposed animals we measured the superoxide anion radical scavenging capacity via photoluminescence. Except of P. abies, exposure to the leachates reduced this antioxidant capacity by approximately 50%. Leachate exposures, except that of Quercus, increased body size and extended lifespan; furthermore, particularly the leachates of both Picea species significantly increased the offspring numbers. This unexpected behavior of exposed Moina may be based on food supplements (e.g., high carbohydrate contents) in the leachates or on yet to be identified regulatory pathways of energy allocation. Overall, our results suggest that the potentially adverse effects of litter leachates can be overruled by either bacterial-growth supporting fractions in the leachates or an internal compensation mechanism in the Moina individuals.