Photodegradation and Biodegradation Study of a Starch and Poly(Lactic Acid) Coextruded Material

To simulate the behavior of agricultural mulch coextruded poly(lactic acid)(PLA)/starch films, two stages were carried out. The first was an ultraviolet treatment (UV) at 315 nm, during which glass transition temperature T_g, weight, and molecular weight (MW) decreased and a separation between PLA and starch phase was observed. For the second stage, the mineralization of the carbon of the material was followed using the ASTM (D 5209–92 and 5338–92) and ISO/CEN (14852 and 14855) standard procedures. To measure the biodegradability of polymer material, the assessment of the carbon balance allowed determination of the distribution between the carbon rate used to the biomass synthesis or the respiration process (released CO₂), as well as the dissolved organic carbon into the culture medium and the carbon in the residual insoluble material. The influence of the nature of the medium and the standardized procedures on the final rate of biodegradation was investigated. Whatever the standardized method, the biodegradation percentage was significantly stronger in liquid medium (92.4–93.4) than on inert medium (80–83%). In the case of the compost process, only released CO₂ was measured and corresponded to 79.1–80.3%.     

Greenhouse gases emissions accounting for typical sewage sludge digestion with energy utilization and residue land application in China

About 20 million tonnes of sludge (with 80% moisture content) is discharged by the sewage treatment plants per year in China, which, if not treated properly, can be a significant source of greenhouse gases (GHGs) emissions. Anaerobic digestion is a conventional sewage sludge treatment method and will continue to be one of the main technologies in the following years. This research has taken into consideration GHGs emissions from typical processes of sludge thickening + anaerobic digestion + dewatering + residue land application in China. Fossil CO₂, biogenic CO₂, CH_4, and avoided CO₂ as the main objects is discussed respectively. The results show that the total CO₂-eq is about 1133 kg/t DM (including the biogenic CO₂), while the net CO₂-eq is about 372 kg/t DM (excluding the biogenic CO₂). An anaerobic digestion unit as the main GHGs emission source occupies more than 91% CO₂-eq of the whole process. The use of biogas is important for achieving carbon dioxide emission reductions, which could reach about 24% of the total CO₂-eq reduction.     

Gasification and its emission characteristics for dried sewage sludge utilizing a fluidized bed gasifier

Various research has attempted to determine the proper treatment of sewage sludge, including thermal technologies. Efficient thermal technologies have been focused on because of their energy saving/energy recovery. Gasification technology can be considered one of these approaches. In this study, the characteristics of gasification reactions were investigated with the aim of finding fundamental data for utilizing sewage sludge as an energy source. For the experiments on sewage sludge gasification reaction characteristics, a laboratory-scale experimental apparatus was set up with a fluidizing bed reactor of 70-mm inner diameter and 600-mm total height using an electric muffle furnace. The experimental materials were prepared from a sewage treatment plant located in Seoul. The reaction temperature was varied from 630 to 860°C, and the equivalence ratio from 0.1 to 0.3. The gas yields, compositions of product gas, and cold gas efficiencies of product gas were analyzed by GC/TCD and GC/FID installed with a carboxen-1000 column. The experimental results indicated that 800°C, ER 0.2 was an optimum condition for sewage sludge gasification. The maximum yield of product gas was about 44%. Producer gas from experiments was mainly composed of hydrogen, carbon monoxide, carbon dioxide, and methane. The cold gas efficiency of sewage sludge gasification was about 68%. The H₂/CO ratio and CO/CO₂ ratio were about 1.1 and 1.4, respectively, in optimum reaction conditions. Gaseous pollutants such as SO₂, HCl, NH₃, H₂S, and NO₂ were also analyzed at various gasification/combustion conditions, and their gaseous products were compared, showing significantly different oxidized product distributions.     

Study of the Degradation of Poly(ethyl glyoxylate): Biodegradation, Toxicity and Ecotoxicity Assays

Biodegradation of poly (ethyl glyoxylate) (PEtG), a functionalized polyacetal, was investigated over 6?month according to ASTM 5988-96 modified method and compared to micronized cellulose. More than 95?% of the polymer was converted into CO₂ over that period attesting the biodegradability of PEtG. The degradation by-products toxicity and ecotoxicity were evaluated. Toxicity was checked using an innovant non-mammalian toxicological model using the nematode Caenorhabditis elegans. Ecotoxicity was performed using a plant growth test with cress (Lepidium Sativum), and barley (Hordeum vulgare). In all cases, results concluded on the harmlessness of PEtG and relative by-products.     

Carbon accounting for Japanese petrochemicals

This paper discusses two bottom-up models for the estimation of carbon storage and CO₂ emissions related to the nonenergy use of fossil energy carriers. The models show how material flow accounting can be applied to policy making. The nonenergy use emission accounting tables model is a static model, while the chemical industry environmental strategy assessment program (CHEAP) model is a dynamic model of the flows of synthetic organic materials. Both models provide detailed and more accurate estimates of carbon storage in materials than the accounting method that is currently used in the framework of the Intergovernmental Panel on Climatic Change (IPCC) guidelines. The results for both models suggest that carbon storage in synthetic organic materials has been overestimated, and consequently CO₂ emissions have been underestimated. Japanese CO₂ emissions in 1996 were at least 1.9% higher than reported previously. The CHEAP model results indicate that the net carbon storage (storage − emissions in waste incineration) will decrease during the next few decades. This decrease is mainly driven by changing waste management practice. Received: December 8, 2000 / Accepted: August 15, 2001     

Morphology of <Emphasis Type="Italic">Penicillium funiculosum</Emphasis> During Biodegradation of Poly (β-hydroxybutyrate-co-β-hydroxyvalerate) [PHBV] with Poly (ε-Caprolactone) [PCL] Blends

Blends of poly (β-hydroxybutyrate-co-β-hydroxyvalerate) with poly (ε-caprolactone) were produced using melt mixing and solvent casting techniques. The biodegradation of blends was tested based in the ASTM G21-90 using Penicillium funiculosum fungal specie. The CO₂ production during biodegradation was measured and fitted using the Gompertz model. Biodegradation of blends varies according to the mixing technique and the proportion of bacterial polymers in the blends. Although lag phase was larger, solvent-casted blends were easier to degrade due to their porous surface and relative lower crystallinity. P. funiculosum morphology during biodegradation appeared to be related to carbon availability i.e. larger and more complex conidiophores, more phialides per conidiophore and the presence of double-phialides, were found in blends with higher PHAs proportion. P. funiculosum morphology was independent to the blending technique used. Hence, morphology of P. funiculosum could be useful as a reference for carbon bioavailability of the blends.     

Kinetics of Aerobic Polymer Degradation in Soil by Means of the ASTM D 5988-96 Standard Method

The standard test method ASTM D 5988-96 for determining the degree and rate of aerobic biodegradation of plastic materials in contact with soil was applied to poly(3-hydroxybutyrate) and poly(-caprolactone). The method proved to be reliable and supplied reproducible measurements of CO₂ production, provided potassium (instead of barium) hydroxide was used as a trapping solution. The trends of CO₂ evolution, as a function of time, observed for the degradation of polymer powders in soil are similar to those predicted by simple first order kinetics in solution. The experimental data are described by a Michaelis–Menten type model, which accounts for the heterogeneity of the polymer-soil system. The kinetic equation deduced predicts the degradation rate to the proportional to the exposed polymer surface area.     

Thermal processing of paper sludge and characterisation of its pyrolysis products

Paper sludge is a waste product from the paper and pulp manufacturing industry that is generally disposed of in landfills. Pyrolysis of paper sludge can potentially provide an option for managing this waste by thermal conversion to higher calorific value fuels, bio-gas, bio-oils and charcoal. This work investigates the properties of paper sludge during pyrolysis and energy required to perform thermal conversion. The products of paper sludge pyrolysis were also investigated to determine their properties and potential energy value. The dominant volatile species of paper sludge pyrolysis at 10 °C/min were found to be CO and CO₂, contributing to almost 25% of the paper sludge dry weight loss at 500 °C. The hydrocarbons (CH₄, C₂H₄, C₂H₆) and hydrogen contributed to only 1% of the total weight loss. The bio-oils collected at 500 °C were primarily comprised of organic acids with the major contribution being linoleic acid, 2,4-decadienal acid and oleic acid. The high acidic content indicates that in order to convert the paper sludge bio-oil to bio-diesel or petrochemicals, further upgrading would be necessary. The charcoal produced at 500 °C had a calorific value of 13.3 MJ/kg.     

Semi-continuous anaerobic co-digestion of thickened waste activated sludge and fat, oil and grease

Co-digestion of thickened waste activated sludge (TWAS) and fat, oil and grease (FOG) was conducted semi-continuously under mesophilic conditions. The results showed that daily methane yield at the steady state was 598 L/kg VS_added when TWAS and FOG (64% of total VS) were co-digested, which was 137% higher than that obtained from digestion of TWAS alone. The biogas composition was stabilized at a CH₄ and CO₂ content of 66.8% and 29.5%, respectively. Micronutrients added to co-digestion did not improve the biogas production and digestion stabilization. With a higher addition of FOG (74% of total VS), the digester initially failed but was slowly self-recovered; however, the methane yield was only about 50% of a healthy reactor with the same organic loading rate.     

On the understanding and control of the spontaneous heating of dried tannery wastewater sludge

We studied the spontaneous heating of dried sludge produced by treating wastewater mainly originating from tanneries. Heating up to burning has been observed in the presence of air and moisture, starting at ambient temperature. To understand and prevent the process we combined chemical and morphological analyses (ESEM) with thermal activity monitoring in insulated vessels. Selective additions of chemicals, either to amplify or depress the reactivity, have been used to investigate and identify both the chemical mechanism causing the sludge self-heating, and a prevention or a mitigation strategy. FeS additions accelerate the onset of reactivity, while S sustains it over time. On the contrary, Ca(OH)₂, Na₂CO₃, NaHCO₃, FeCl₂, EDTA, NaClO can limit, up to completely preventing, the exothermic activity. All the experimental evidences show that the reactions supporting the dried sludge self-heating involve the Fe/S/O system. The total suppression of the reactivity requires amounts of additives that are industrially incompatible with waste reduction and economics. The best prevention requires reduction or removal of S and Fe from the dried solid matrix.     

Feasibility of greenhouse gas emissions offsets for natural source zone depletion of petroleum hydrocarbons

Hydrocarbon biodegradation is an important process for remediating petroleum hydrocarbons and managing large sites. However, this biodegradation results in what are essentially unavoidable CO₂ emissions to the atmosphere. A feasibility assessment was conducted to quantitatively consider reuse options for petroleum brownfields that would offset contaminant respiration emissions rates in the 2 to 10 micromoles CO₂ per meters squared per second (μmol CO₂ m^?2 s^?1) typically observed. Under a wide range of solar resource scenarios, placement of solar panels over only a fraction (no more than 35%) of the site footprint is estimated as necessary to achieve an emissions offset. Similarly, placement of one 30‐meter tall wind turbine of moderate rating (approximately 30 to 50 kW) is sufficient to provide an offset for a nominal 1,000 square meters site. For spreading of spent calcium‐rich construction materials, under even a high emissions scenario, the required footprint for the offset is less than the site footprint. While these approaches appear feasible, revegetation as forestland is estimated as sufficient only at contaminant respiration rates up to 2 μmol CO₂ m^?2 s^?1. Revegetation as rangeland and cropland, which sequesters CO₂ mainly in soil organic carbon, is estimated as requiring more than the site footprint under many contaminant respiration rates. Revegetation as a wetland fares slightly better from a carbon storage perspective, but it also has the potential for N₂O and CH₄ emissions that may largely undo the benefit from sequestration in soil organic matter. Overall, the results indicate several methods that are viable for achieving emissions offsets and a quantitation method that can be honed with site‐specific input parameters as appropriate.     

Analysis of the combustion and pyrolysis of dried sewage sludge by TGA and MS

In this study, the combustion and pyrolysis processes of three sewage sludge were investigated. The sewage sludge came from three wastewater treatment plants.Proximate and ultimate analyses were performed. The thermal behaviour of studied sewage sludge was investigated by thermogravimetric analysis with mass spectrometry (TGA-MS). The samples were heated from ambient temperature to 800 °C at a constant rate 10 °C/min in air (combustion process) and argon flows (pyrolysis process). The thermal profiles presented in form of TG/DTG curves were comparable for studied sludges. All TG/DTG curves were divided into three stages. The main decomposition of sewage sludge during the combustion process took place in the range 180–580 °C with c.a. 70% mass loss. The pyrolysis process occurred in lower temperature but with less mass loss. The evolved gaseous products (H₂, CH₄, CO₂, H₂O) from the decomposition of sewage sludge were identified on-line.     

Groundwater treatment and aquatic toxicity reduction at a chemical production site

Contaminated groundwater at a chemical antioxidant and phenolic resin chemical production site was subjected to treatability studies to develop design criteria for surface water discharge. Raw groundwater required pretreatment for total suspended solids (TSS) and color removal prior to treatment by ultraviolet light/hydrogen peroxide (UV/H₂O₂). Because of high capital and operating costs for UV/H₂O₂, biological treatment was evaluated as an alternate. Respirometric analyses showed that completely mixed activated sludge could be applied as a treatment technology to the groundwater. Biotreatment resulted in an approximately 70 percent reduction in soluble chemical oxygen demand (SCOD). Residual SCOD was recalcitrant to further biodegradation. The treated effluent was tested for aquatic toxicity using fathead minnows (Pimephales promelas) and Ceriodaphnia dubia and was found to be toxic. Toxicity reduction of biotreatment effluent was evaluated in bench-scale experiments using activated carbon adsorption, filtration, and UV/H₂O₂. Subsequent toxicity testing showed that filtration alone could reduce the bioeffluent toxicity and that residual SCOD was not the primary source of toxicity.     

Life-cycle greenhouse gas emissions and economic analysis of alternative treatments of solid waste from city markets in Vietnam

We utilize life cycle assessment to trace conversion of degradable organic carbon (DOC) contained in organic waste from city markets in Da Nang, Vietnam. Our methodology makes explicit the process of conversion of DOC under aerobic and anaerobic conditions, as well as the balance of nutrients. Greenhouse gas emissions were calculated for six alternative scenarios: (i) anaerobic landfilling (current situation); (ii) semi-aerobic landfilling; (iii) landfill gas capture; (iv) composting; (v) pre-composting before landfill; and (vi) biogas production. We calculate that 1 t of waste in anaerobic landfilling emits 1.70 t CO₂-eq. with life-cycle perspective. Lowest emission occurs in biogas scenario with 0.26 t CO₂-eq./t. Composting occupies an intermediate position with 0.39 t CO₂-eq./t. Likewise, we estimate that cost of emission reduction in solid waste sector of Vietnam is 15.13 US$/t CO₂-eq., given by alternative of composting and taking anaerobic landfilling as reference. On the other hand, if social cost of carbon (SCC) is incorporated lowest cost to treat 1 t of waste is given by composting and semi-aerobic landfilling at discount rate of 5 %. However, using lower discount rates, and consequently higher values of SCC, composting and biogas production become the alternatives with lowest treatment costs.     

Biomass Carbon Ratio of Polymer Composites Measured by Accelerator Mass Spectrometry

The evaluation method of biomass carbon ratio of polymer composite samples including organic and inorganic carbons individually was investigated. Biodegradable plastics and biobased plastics can have their mechanical properties improved by combining with inorganic fillers. Polymer composites consisting of biodegradable plastics and carbonate were prepared by two different methods. Poly(lactic acid) (PLA) composite was prepared by synthesis from l-lactide with catalyst and calcium carbonate (CaCO₃) powders from lime. Poly(butylene succinate) (PBS) composite was prepared by hot-pressing the mixture of PBS powder and CaCO₃ powders from oyster shells. The mechanical properties of composite samples were investigated by a tensile test and a compression test using an Instron type mechanical tester. Tensile test with a dumbbell shape specimen was performed for PBS composite samples and compression test with a column shape specimen for PLA composite samples. Strength, elastic modulus and fracture strain were obtained from the above tests. Biomass carbon ratio is regulated in the American Standards for Testing and Materials (ASTM). In ASTM standards on biomass carbon ratio, it is required that carbon atoms from carbonates, such as CaCO₃, are omitted. Biomass carbon ratio was evaluated by ratio of ¹⁴C to ¹²C in the samples using Accelerator Mass Spectrometry (AMS). The effect of pretreatment, such as oxidation temperature and reaction by acid, on results of biomass carbon ratio was investigated. Mechanical properties decrease with increasing CaCO₃ content. The possibility of an evaluation method of biomass carbon ratio of materials including organic and inorganic carbons was shown.     

Biodegradation of LDPE/Modified Starch Blends Sterilized with Gamma Radiation

Blends of LDPE/modified starch were prepared, sterilized by gamma radiation and investigated with respect to their microbial degradation by a mixture of fungal strains in liquid medium after 90 days, was analyzed by carbon dioxide (CO₂) production (Sturm test). Biodegradation of blends was evaluated by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction; mechanical testing, scanning electron microscopy (SEM). The biodegradation of LDPE/modified starch blends was attributed to microbiological attack, with alterations in the chemical structure of the blend with an increase in the carbonyl and vinyl indices and the appearance of new crystalline symmetry generating a crystalline domain not existing before in the blend and decrease in the mechanical properties.     

CO₂ emission factors for waste incineration: Influence from source separation of recyclable materials

CO₂-loads from combustible waste are important inputs for national CO₂ inventories and life-cycle assessments (LCA). CO₂ emissions from waste incinerators are often expressed by emission factors in kg fossil CO₂ emitted per GJ energy content of the waste. Various studies have shown considerable variations between emission factors for different incinerators, but the background for these variations has not been thoroughly examined. One important reason may be variations in collection of recyclable materials as source separation alters the composition of the residual waste incinerated. The objective of this study was to quantify the importance of source separation for determination of emission factors for incineration of residual household waste. This was done by mimicking various source separation scenarios and based on waste composition data calculating resulting emission factors for residual waste routed to incineration. Emission factors ranged from 27 to 40 kg CO₂/GJ. The results appeared most sensitive towards variations in waste composition and water content. Recycling rates and lower heating values could not be used as simple indicators of the resulting emission factors for residual household waste; however the fossil carbon ratio of the waste after source separation was found to be appropriately correlated with the emission factor. Based on the results, it is recommended to carefully evaluate the source separation and collection systems behind reported literature values when comparing different studies and when using the values for environmental assessment purposes.     

Carbon isotope forensics for methane source identification

Methane (CH₄) in ecosystems originates from ancient petroleum formed deep within the earth and/or via microbial fermentation of organic carbon and subsequent reduction of carbon dioxide (CO₂). Given the complexity of different ecosystems, origins of CH₄ present can be difficult to determine. This issue was realized in a situation where an antimethanogenic in situ chemical reduction (ISCR) remedial amendment containing organic carbon plus zero‐valent iron was applied to treat chlorinated solvents in groundwater at a former dry cleaner facility. The technology rapidly and effectively reduced the concentration of tetrachloroethene in groundwater thus meeting project goals without the stoichiometric accumulation of catabolites such as trichloroethene (TCE), cis‐1,2‐dichloroethene, or vinyl chloride and without excessive methanogenesis (e.g., <2 mg/L) in the treated area. However, approximately 9 months after treatment, increased levels of CH₄ (from 5 to 10 mg/L) were observed downgradient from the treated area. The applied remedial amendment contained approximately 60% (weight basis) fermentation organic carbon and was therefore a potential source of this CH₄. However, there was <500 mg/L total organic carbon in groundwater emanating from the upgradient treatment area which was unlikely sufficient to produce that much CH₄. Moreover, the soil gas also contained benzene, toluene, ethylbenzene, and xylenes and other gasoline constituents. These data suggested that the presence of three gasoline/diesel underground storage tanks that were previously closed in place with no active remediation performed could be the source of elevated CH₄. Thirdly, there were sewer lines, utilities, multiple gasoline stations, and industrial activities in the immediate area. With an initial assumption that CH₄ source(s) could include the ISCR amendment over stimulation of production, gasoline sourced CH₄ from nearby leaking lines, or sewage from local fractured pipes, carbon isotope analyses—radiocarbon (Δ¹⁴C) and stable carbon (δ¹³C)—were coupled with CH₄ and CO₂ concentration data from groundwater samples to determine the origin of respired carbon. The δ¹³C range for carbon sources respired in the process would be approximately ?26.5‰ to ?33.0‰ for the ISCR amendment and total petroleum hydrocarbons (TPH) residuals, respectively. Δ¹⁴C is approximately 0‰ and ?999‰ for the ISCR amendment (young carbon) and TPH (old carbon), respectively. The isotopic signature of respired gasses confirmed that elevated CH₄ downgradient of the treated area originated primarily from sewer gasses (or fermentation of liquids released from sewer lines). This study provides an overview of the capability to apply carbon isotope geochemistry to confirmation of remedial protocols and sources of anthropogenic carbon pools that conclusively identify the origin of CH₄ in a complex ecosystem undergoing a remedial action.     

Microbial biomass yield and turnover in soil biodegradation tests: carbon substrate effects

Most of the standardized biodegradation tests used to assess the ultimate biodegradation of environmentally degradable polymers are based solely on the determination of net evolved carbon dioxide. However, under aerobic conditions, it has to be considered that heterotrophic microbial consortia metabolize carbon substrates both to carbon dioxide and in the production of new cell biomass. It is generally accepted that in the relatively short term, 50% of the carbon content of most organic substrates is converted to CO₂, with the remaining carbon being assimilated as biomass or incorporated into humus. The latter is particularly important when the metabolism of the organic matter occurs in a soil environment. A straightforward relationship between the free-energy content of a carbon substrate (expressed as the standard free-energy of combustion) and its propensity for conversion to new microbial biomass rather than mineralization to CO₂ has been established. This can potentially lead to underestimation of biodegradation levels of test compounds, especially when they consist of carbon in a fairly low formal oxidation state and relatively high free-energy content. In the present work, the metabolism of different kind of carbon substrates, especially in soil, is reviewed and compared with our own experimental results from respirometric tests. The results show that conversion of highly oxidized materials, such as the commonly used reference materials, cellulose or starch, to CO₂ may be significantly overestimated. The addition of glucosidic material to soil leads to greatly increased respiration and is accompanied by a very low conversion to biomass or humic substances. In contrast, relatively less oxidized substrates metabolize more slowly to give both CO₂ and biomass to an extent which may be significantly underestimated if glucosidic materials are used as the reference. The need for an overall carbon balance taking into account both the carbon immobilized as biomass and that volatized as CO₂ must be considered in standard respirometric procedures for assessing the biodegradability of slowly degrading macromolecules.     

Hydrogen production from food wastes and gas post-treatment by CO2 adsorption

The production of H₂ by biological means, although still far from being a commercially viable proposition, offers great promise for the future. Purification of the biogas obtained may lead to the production of highly concentrated H₂ streams appropriate for industrial application. This research work evaluates the dark fermentation of food wastes and assesses the possibility of adsorbing CO₂ from the gas stream by means of a low cost biomass-based adsorbent. The reactor used was a completely stirred tank reactor run at different hydraulic retention times (HRTs) while the concentration of solids of the feeding stream was kept constant. The results obtained demonstrate that the H₂ yields from the fermentation of food wastes were affected by modifications in the hydraulic retention time (HRT) due to incomplete hydrolysis. The decrease in the duration of fermentation had a negative effect on the conversion of the substrate into soluble products. This resulted in a lower amount of soluble substrate being available for metabolisation by H₂ producing microflora leading to a reduction in specific H₂ production.Adsorption of CO₂ from a gas stream generated from the dark fermentation process was successfully carried out. The data obtained demonstrate that the column filled with biomass-derived activated carbon resulted in a high degree of hydrogen purification. Co-adsorption of H₂S onto the activated carbon also took place, there being no evidence of H₂S present in the bio-H₂ exiting the column. Nevertheless, the concentration of H₂S was very low, and this co-adsorption did not affect the CO₂ capture capacity of the activated carbon.