Degradation of Cellulose Acetate-Based Materials: A Review

Cellulose acetate polymer is used to make a variety of consumer products including textiles, plastic films, and cigarette filters. A review of degradation mechanisms, and the possible approaches to diminish the environmental persistence of these materials, will clarify the current and potential degradation rates of these products after disposal. Various studies have been conducted on the biodegradability of cellulose acetate, but no review has been compiled which includes biological, chemical, and photo chemical degradation mechanisms. Cellulose acetate is prepared by acetylating cellulose, the most abundant natural polymer. Cellulose is readily biodegraded by organisms that utilize cellulase enzymes, but due to the additional acetyl groups cellulose acetate requires the presence of esterases for the first step in biodegradation. Once partial deacetylation has been accomplished either by enzymes, or by partial chemical hydrolysis, the polymer’s cellulose backbone is readily biodegraded. Cellulose acetate is photo chemically degraded by UV wavelengths shorter than 280 nm, but has limited photo degradability in sunlight due to the lack of chromophores for absorbing ultraviolet light. Photo degradability can be significantly enhanced by the addition of titanium dioxide, which is used as a whitening agent in many consumer products. Photo degradation with TiO₂ causes surface pitting, thus increasing a material’s surface area which enhances biodegradation. The combination of both photo and biodegradation allows a synergy that enhances the overall degradation rate. The physical design of a consumer product can also facilitate enhanced degradation rate, since rates are highly influenced by the exposure to environmental conditions. The patent literature contains an abundance of ideas for designing consumer products that are less persistent in the outdoors environment, and this review will include insights into enhanced degradability designs.     

Combined application of non-discriminated conventional pyrolysis and tetramethylammonium hydroxide-induced thermochemolysis for the characterization of the molecular structure of humic acid isolated from polluted sediments from the Ravenna Lagoon

Humic acid (HA) isolated from highly polluted sediment from the Ravenna Lagoon (Italy) was subjected to pyrolysis/tetramethylammonium hydroxide (TMAH)-induced thermochemolysis to reveal the impact of industrial activities on humification. Special effort was made to distinguish between analytes originating from the polymeric humic organic matter network along with sequestered compounds (which cannot be released by solvent extraction), and the solvent-extractable lipid fraction sorbed onto the organic matrix. Exhaustive solvent extraction of the isolated HA proved mandatory to avoid biased results when identifying the origin of the pyrolyzates of untreated samples. Conventional pyrolysis at 750 degrees C of the "degreased" HA revealed a characteristic polycyclic aromatic hydrocarbon (PAH) pattern, which was significantly different than patterns obtained from the pyrolysis of natural humic acids. TMAH-induced thermochemolysis at 500 degrees C provided information on carboxylic acids covalently bound inside the HA network via ester bonds. Thermochemolysis of the "degreased" matrix at 750 degrees C, resulting in the cleavage of C-O and C-C bonds, revealed a significant PAH pattern very similar to that obtained by conventional pyrolysis. The uncommon PAH pattern points to the formation of bound residues as the humification/detoxification pathway. Recalcitrant hopane hydrocarbons showed very similar patterns for both the untreated and exhaustively solvent-extracted samples, which points to hopanes being linked inside the humic network via C-C bonds. The technique of non-discriminating flash pyrolysis used in this study, based on extremely rapid capacitive discharge heating in a Silcosteel capillary, proved to be an excellent method to obtain high-boiling pyrolyzates (PAHs beyond 252Da molecular weight, C(29)-C(31)-hopanes).     

Integrated regional modelling and scenario development to evaluate future water demand under global change conditions

Within climate change impact research, the consideration of socioeconomic processes remains a challenge. Socioeconomic systems must be equipped to react and adapt to global change. However, any reasonable development or assessment of sustainable adaptation strategies requires a comprehensive consideration of human-environment interactions. This requirement can be met through multi-agent simulation, as demonstrated in the interdisciplinary project GLOWA-Danube (GLObal change of the WAter Cycle; ). GLOWA-Danube has developed an integrated decision support tool for water and land use management in the Upper Danube catchment (parts of Germany and Austria, 77,000 km²). The scientific disciplines invoked in the project have implemented sixteen natural and social science models, which are embedded in the simulation framework DANUBIA. Within DANUBIA, a multi-agent simulation approach is used to represent relevant socioeconomic processes. The structure and results of three of these multi-agent models, WaterSupply, Household and Tourism, are presented in this paper. A main focus of the paper is on the development of global change scenarios (climate and society) and their application to the presented models. The results of different simulation runs demonstrate the potential of multi-agent models to represent feedbacks between different water users and the environment. Moreover, the interactive usage of the framework allows to define and vary scenario assumptions so as to assess the impact of potential interventions. It is shown that integrated modelling and scenario design not only provide valuable information, but also offer a platform for discussing complex human-environment-interactions with stakeholders.     

Extremophiles: from abyssal to terrestrial ecosystems and possibly beyond

The anthropocentric term “extremophile” was introduced more than 30 years ago to describe any organism capable of living and growing under extreme conditions—i.e., particularly hostile to human and to the majority of the known microorganisms as far as temperature, pH, and salinity parameters are concerned. With the further development of studies on microbial ecology and taxonomy, more “extreme” environments were found and more extremophiles were described. Today, many different extremophiles have been isolated from habitats characterized by hydrostatic pressure, aridity, radiations, elevated temperatures, extreme pH values, high salt concentrations, and high solvent/metal concentrations, and it is well documented that these microorganisms are capable of thriving under extreme conditions better than any other organism living on Earth. Extremophiles have also been investigated as far as the search for life in other planets is concerned and even to evaluate the hypothesis that life on Earth came originally from space. Extremophiles are interesting for basic and applied sciences. Particularly fascinating are their structural and physiological features allowing them to stand extremely selective environmental conditions. These properties are often due to specific biomolecules (DNA, lipids, enzymes, osmolites, etc.) that have been studied for years as novel sources for biotechnological applications. In some cases (DNA polymerase, thermostable enzymes), the search was successful and the final application was achieved, but certainly further exploitations are next to come.     

Investigation of the solvent extracts of humic organic matter (HOM) isolated from the Ravenna Lagoon to study environmental pollution and microbial communities

Solvent extracts of HOM isolated from highly polluted sediments from the Ravenna Lagoon were studied. Diagnostic indicators included polycyclic aromatic hydrocarbons (PAHs) and nonylphenols as hazardous organic pollutants to characterize anthropogenic pollution, as well as fatty acids (FA, analysed as methyl esters, FAME) to characterize microbial communities responsible for natural attenuation processes. The distribution of PAHs including cyclopentafused surrogates pointed to a significant pyrogenic origin, characteristic for methane combustion. The PAH distribution was characterized by high concentrations of highly carcinogenic analytes with molecular weights of 276Da (benzo[ghi]perylene prevailing) and 300Da (coronene prevailing). The PAH pattern as obtained by solvent extraction was very different from that obtained from pyrolysis/thermochemolysis of the HOM polymeric matrix. The FA pattern indicated strong bacterial input, with a significant contribution from methanotrophic bacteria as revealed by monounsaturated members with n:1omega8 and n:1omega5 double bonds in the alkyl chain. Terrestrial inputs as revealed by FAME analysis beyond C(20) with pronounced even-over-odd discrimination were of minor significance. This was confirmed by the pattern of nC(24)-nC(30) alcohols in strong even-over-odd prevalence occurring in relatively low concentrations. The hopane hydrocarbon distribution reflected a distinctive impact from industrial processes utilizing heavy fractions of petroleum as feedstock. Hopanols along with the 17beta(H),21beta(H)-bishomohopanoic acid pointed to hopane producers, including methanotrophic and sulfate-reducing bacteria. Nonylphenols, which could not be detected in the pyrograms of solvent-extracted HOM matrix, had a total concentration of about 70microg g(-1) referred to the HOM in the solvent extract. In addition to common phytosterols including beta-sitosterol, coprostanol could be detected in the solvent extracts pointing to human fecal matter contamination. Concentration of resin acids turned out to be very low, thus no harmful environmental effects are to be expected from these compounds.     

Biomonitoring of persistent organochlorine pesticides, PCDD/PCDFs and dioxin-like PCBs in blood of children from South West Germany (Baden-Wuerttemberg) from 1993 to 2003

In the context of a monitoring program, persistent organic pollutants (POPs) were quantified in the blood of 10 year old children at four different demographic regions in Baden-Wuerttemberg, a highly industrialised federal state in South West Germany. DDE, HCB, PCB 138, PCB 153 and PCB 180 were measured in 1996/1997, 1998/1999, 2000/2001 and 2002/2003 in individual samples of about 400 children per year. PCDD/PCDFs and some relevant coplanar PCBs were determined in pooled samples from children in seven cycles from 1993 to 2003. Blood concentrations of the investigated compounds decreased in that time period by a factor of 2-4 with the exception of most PCDFs. The concentrations of POPs in the blood of the children were distinctly lower than the concentrations reported for adults. Breast feeding was associated with about 30% higher median concentrations of DDE, HCB, PCBs and a 30% increase for mean PCDD/PCDF concentrations. Concerning demographic differences, significant lower concentrations of HCB, PCBs and PCDD/PCDFs could be seen in children from Mannheim compared to the region of Aulendorf. About 10-20% higher concentrations were found in boys compared to girls for HCB, indicator PCBs and PCDD/PCDFs. The pattern of non-ortho and mono-ortho PCBs in the blood of children was similar to the pattern reported for mother's milk, and PCB 126 and PCB 156 contributed about 70% to the toxicity of dioxin-like PCBs and about one-third to total TEQ including PCDD/PCDFs.