Synthesis and Modeling of Poly(L-lactic acid) via Polycondensation of L-Lactic Acid.

We present synthetic experiments of lactic acid (LA) polycondensation to produce poly(lactic acid) (PLA) as well as kinetic modeling calculations that capture the polymer molecular weight increase with time, given the initial concentrations. Tin-octoate-catalyzed polycondensation of (D,L)- or L-lactic acid was carried out in pre-dried toluene after azeotropic dehydration for 48-120 h at 130-137 °C. The polymerization was optimized by varying lactic acid and catalyst concentrations as well as the temperature. Gel permeation chromatography was used to experimentally follow the evolution of molecular weights and the products were characterized by NMR, TGA, DSC and IR. Under optimal conditions, PLLA with weight-average molecular weight (Mw) of 161 kDa could be obtained. The rate equations that describe polycondensation kinetics were recast in a condensed form that allowed very fast numerical solution and calculation of the number-average molecular weight with time. Deviations with respect to the experiment were minimized in a least-squares fashion to determine rate constants. The optimized kinetics parameters are shown to reproduce the experimental data accurately.

A web-based GIS platform supporting innovative irrigation management techniques at farm-scale for the Mediterranean island of Crete.

The aim of this paper is the creation of an integrated and free-access web platform for parcel irrigation water management on a large spatial scale (Water District of Crete, in Greece) in order to: a) accurately determine the irrigation needs of the main crops for Crete such as olives, citrus, avocados and vineyards, b) design strategies, for optimal adaptation of the agricultural sector in the context of climate change, and c) incorporate the dynamic integration of the above information through the creation of a digital platform. In the proposed decision-making system, essential factors are taken into account, such as real-time meteorological data, information about the type and spatial distribution of the agricultural parcels in Crete, algorithms for calculation crop evapotranspiration per development stage and age of the crops, satellite remote sensing techniques in combination with field surveys to depict accurate soil texture map for the whole island of Crete as well as sustainable cultivation practices for saving water per crop and parcel geomorphology. Based on the proposed decision-making system, users will have the opportunity in any specific location/farm in Crete to know the irrigation needs of the crops in real-time and obtain information about proper climate-water adaptation practices. The main novelty points of the proposed platform include the derivation of parcel-level soil texture data from Sentinel-2 satellite imagery and field samples, the comprehensiveness of the irrigation management information, the relatively low data requirements and the application interface simplicity provided to the end-user.

In vitro digestion and microbial fermentation of dried food residues, a potential "new" component for pet food, and different non-digestible carbohydrate sources.

Food residues are often fed to dogs in private households and might also be a potential "new" ingredient for pet food in the future. As food residues might contain not only digestible, but also fermentable substrates, an effect on the intestinal microbiota can be assumed. In the present study, two batches of dried food residues (DFR) collected from hotels in Crete were microbially fermented in an in vitro batch culture system with canine fecal inoculum: non-sterile DFR including meat (DFRm), sterile DFR including meat (DFRms) and sterile DFR without meat (DFRwms). Different non-digestible carbohydrate sources (beet pulp, wheat bran, inulin, carrot pomace, brewer´s spent grains, cellulose and lignocellulose) were included for comparison. Inulin, cellulose and lignocellulose were only used as raw materials, while the other test substrates were incubated as raw and enzymatically pre-digested substrates. After incubation for 24 hours, the raw food residues markedly increased the concentrations of bacterial metabolites in the fermenters, although smaller effects were observed for the DFRwms. When the enzymatically pre-digested food residues were incubated, the effects were more pronounced for the DFRms and DFRwms. In general, when compared with the other test substrates, the food residues were microbially fermented to a comparable or partly higher extent. Interestingly, high n-butyrate concentrations were measured in the inocula, both after incubation of the raw and pre-digested food residues. In conclusion, the food residues contained enzymatically digestible and microbially fermentable substrates. If considered as a potential future ingredient for pet food, a standardization of the collection and processing of food residues might be necessary in order to reduce compositional variability and varying effects on the intestinal microbiota.

Impact of the dietary inclusion of dried food residues on the apparent nutrient digestibility and the intestinal microbiota of dogs.

The use of food residues for animal nutrition might imply ecological and economic advantages; however, their effects as a potential ingredient have not yet been evaluated in dogs. In the present study, four diets with 0, 5, 10 and 15% dried food residues (DFR), derived from hotel catering, were fed to 10 healthy adult dogs. At the end of each three-week feeding period, faeces and blood were collected. The apparent nutrient digestibility was calculated by the dietary inclusion of titanium dioxide as an inert marker. The results demonstrated that the apparent crude protein digestibility and ether extract digestibility decreased with increasing amounts of DFR in the diets (p < 0.05). In addition, an increase of the faecal concentrations of acetic acid, propionic acid, n-butyric acid and total short-chain fatty acids (SCFA) was observed (p < 0.05). Faecal ammonium and lactate concentrations, as well as plasma phenol and indole concentrations, were not linearly affected by the dietary inclusion of DFR. The relative abundance of Fusobacteria in the faeces of the dogs decreased, and the relative abundance of Actinobacteria and Bacteroidetes increased with increasing amounts of DFR in the diets (p < 0.05). In conclusion, the DFR seemed to be intensively fermented by the intestinal microbiota of the dogs, as indicated by the increased faecal SCFA concentrations and the shifts in the composition of the faecal microbiota. Dietary inclusion levels of up to 5% can be recommended based on our results, as the observed lower apparent crude protein and ether extract digestibility might limit the use of food residues for dogs at higher amounts.

Bioactive Compounds in Food Waste: A Review on the Transformation of Food Waste to Animal Feed.

Bioactive compounds are substances which are present in foods in small amounts and have the ability to provide health benefits. Bioactive compounds include but are not limited to long-chain polyunsaturated fatty acids, vitamins, carotenoids, peptides, and polyphenols. The aim of the present study is to review literature for potential bioactive compounds present in food waste material and discuss the transformation of food waste to animal feed under the perspective that usage of food waste, rather than disposal, may tackle food insecurity and provide health benefits. Finally, applications in poultry and swine nutrition, with emphasis on the presence of fatty acids on food waste material, are discussed.

Innovative methodology for the prioritization of the Program of Measures for integrated water resources management of the Region of Crete, Greece.

An innovative multi-criteria methodology was proposed for the prioritization of the Program of Measures (PoM) in the Water Region of Crete, and applied specifically to the basin of Geropotamos river according to the requirements of the Water Framework Directive. This study relied on the four pillars of sustainability and the EU cross-compliance legislative objective for the minimization of the climate change impact. The multi-criteria evaluation methodology was based on the results of four different types of analyses: a DPSIR analysis, a SWOT analysis, a Cost-Benefit Analysis and a climate change impacts analysis. Public participation on the results of the study with local stakeholders was used at every stage of the multi-criteria evaluation process, from the selection and weighing of the criteria to the final ranking and measures' prioritization. The PoM contains two types of measures: basic measures which deal with the implementation of existing legislation and are the same for all regions of Greece and additional measures which are specified for the Region of Crete. The results of the prioritization process in Geropotamos Basin suggests that improving the water quality and ecological status of available water resources do not always require significant financial resources and can have a high impact in terms of achieving "good" quality status.

Use of halophytes in pilot-scale horizontal flow constructed wetland treating domestic wastewater.

Recent findings encourage the use of halophytes in constructed wetlands for domestic wastewater treatment due to their special physiological characteristics as the ability to accumulate heavy metals and salts in their tissues makes them ideal candidates for constructed wetland vegetation. In this particular study, we investigated the application of halophytic plants in a horizontal flow constructed wetland for domestic wastewater treatment purposes. The pilot plant which was situated in Crete (Greece) was planted with a polyculture of halophytes (Tamarix parviflora, Juncus acutus, Sarcocornia perrenis, and Limoniastrum monopetalum). The system's performance was monitored for a period of 11 months during which it received primary treated wastewater from the local wastewater treatment plant. Results show that halophytes developed successfully in the constructed wetland and achieved organic matter and pathogen removal efficiencies comparable to those reported for reeds in previous works (63% and 1.6 log units, respectively). In addition, boron concentration in the effluent was reduced by 40% in comparison with the influent. Salinity as expressed by electrical conductivity did not change during the treatment, indicating that the accumulation of salts in the leaves is not able to overcome electrical conductivity increasing due to evapotranspiration. The results indicate an improvement in the treatment of domestic wastewater via the use of halophyte-planted CWs.

Deployment of municipal solid wastes as a substitute growing medium component in marigold and basil seedlings production.

The possible use of municipal solid waste compost (MSWC) in the production of marigold and basil seedlings examined. Six medium prepared from commercial peat (CP) and MSWC (0, 15, 30, 45, 60, and 100% v/v). There was not any plant growth when MSWC used alone (100%). The addition of MSWC in low content (15% and 30%) improved seed emergence for marigold and basil respectively, while greater content revealed opposed impacts. Mean emergence time delayed as MSWC content increased into substrates. Addition of MSWC (especially in content greater than 30%) into CP reduced (from 34 to 64%) plant height, leaf number and stem diameter as a consequence reduced plant fresh weight (plant biomass) for both species. The number of lateral stems decreased (up to 81%) in basil when MSWC added into substrate mixtures. Chlorophyll b content decreased (up to 58%) in substrates with MSWC content greater than 15% or 30% while similar reduction observed in content of Chlorophyll a and total carotenoids for basil with MSWC > 60%. However, Chlorophyll a and total carotenoids content increased as MSWC content increased for marigold. K and Na leaf content increased but P equivalent decreased as MSWC content increased. Nursery-produced basil and marigold seedlings grown in 15% MSWC; displayed quality indices similar to those recorded for conventional mixtures of peat and may act as component substitute.

Use of fertigation and municipal solid waste compost for greenhouse pepper cultivation.

Municipal solid waste compost (MSWC) and/or fertigation used in greenhouse pepper (Capsicum annuum L.) cultivation with five different substrates with soil (S) and/or MSWC mixtures (0-5-10-20-40%) used with or without fertigation. Plants growth increased in 10-20% MSWC and fertigation enhanced mainly the plant height. Fruit number increased in S : MSWC 80 : 20 without fertilizer. Plant biomass increased as MSWC content increased. There were no differences regarding leaf fluoresces and plant yield. The addition of MSWC increased nutritive value (N, K, P, organic matter) of the substrate resulting in increased EC. Fruit fresh weight decreased (up to 31%) as plants grown in higher MSWC content. Fruit size fluctuated when different MSWC content used into the soil and the effects were mainly in fruit diameter rather than in fruit length. Interestingly, the scale of marketable fruits reduced as MSWC content increased into the substrate but addition of fertilizer reversed this trend and maintained the fruit marketability. MSWC affected quality parameters and reduced fruit acidity, total phenols but increased fruit lightness. No differences observed in fruit dry matter content, fruit firmness, green colour, total soluble sugars and EC of peppers and bacteria (total coliform and E. coli) units. Low content of MSWC improved plant growth and maintained fruit fresh weight for greenhouse pepper without affecting plant yield, while fertigation acted beneficially.

Assessing odour nuisance from wastewater treatment and composting facilities in Greece.

The problem of odour nuisances in Greece was explored using: (a) field measurements of a range of malodorous compounds (hydrogen sulfide, ammonia, benzene, toluene, xylenes, formaldehyde, acetaldehyde, acetone, methyl-mercaptan and carbonyl sulfide) from selected wastewater treatment plants and composting facilities; and (b) questionnaires, completed by wastewater treatment plant operators, to investigate potential odour problems, the odour abatement technologies used, and potential interest and motives for adopting such technologies. The sparse information available in the literature is also exploited. Results indicate that on several occasions there was an odour problem, often stemming from the uncontrolled city sprawl, which results in mixed and often conflicting land uses. This is particularly true for wastewater treatment plants, which tend to be built close to built-up areas and highlights the importance of town planning as a tool to minimize odour problems. Measurement of odours and/or odour related gases is not commonly practised in Greece, while the odour abatement systems currently used are often considered inadequate by plant managers who do have an active interest in using more efficient and effective technologies. To our knowledge, this is the first systematic effort to monitor the odour nuisance in the country.

Construction simplicity and cost as selection criteria between two types of constructed wetlands treating highway runoff.

Two free water surface (FWS) and two subsurface flow (SSF) pilot-size wetlands were constructed for the evaluation of their performance in treating highway runoff (HRO) in the heart of the Mediterranean region, the island of Crete, at the southernmost point of Greece. Detailed recordings of the resources involved during the construction allowed a thorough calculation of the cost of the systems and the requirements in materials, man-hours, and equipment. The two identical FWS systems had a surface area of 33 m(2) each, while the two identical SSF covered 32 m(2) each. One FWS and one SSF, named FWS12 and SSF12, respectively, were designed with a hydraulic retention time (HRT) of 12 h, with each one capable of treating a maximum HRO of 12.6 m(3)/day. The other couple, named FWS24 and SSF24, respectively, was designed with an HRT of 24 h, with each receiving a maximum HRO of 6.3 m(3)/days. An influent storage tank was required to hold the runoff during the common storm events and control the flow rate (and the hydraulic retention time) into the wetlands. This construction represented 25% of the total construction cost, while 5% was spent on the influent automated (and sun-powered) control and distribution system, from the storage tank to the wetlands. The respective total cost allocated to the two SSF systems (euro 14,676) was approximately 10% higher than that of the FWS (euro 13,596), mainly due to the three different-sized gravel layers used in the SSF substrate compared to the topsoil used in the FWS, which tripled the cost and placement time. The Total Annual Economic Cost (TAEC) was euro 1799/year and euro 1847/year for the FWS and SSF pair, respectively. TAEC was also used to compare the economic efficiency of the systems per cubic meter of HRO treated and kilograms of COD and TSS removed from the wetlands during their first operational year. Based on these estimations, FWS12 recorded the lowest TAEC(COD) and TAEC(TSS) values (euro 89.09/kg and euro 43.69/kg, respectively) compared to the other three systems, presenting a more economically favorable option.

Investigation of the microbial community structure and activity as indicators of compost stability and composting process evolution.

In a bid to identify suitable microbial indicators of compost stability, the process evolution during windrow composting of poultry manure (PM), green waste (GW) and biowaste was studied. Treatments were monitored with regard to abiotic factors, respiration activity (determined using the SOUR test) and functional microflora. The composting process went through typical changes in temperature, moisture content and microbial properties, despite the inherent feedstock differences. Nitrobacter and pathogen indicators varied as a monotonous function of processing time. Some microbial groups have shown a potential to serve as fingerprints of the different process stages, but still they should be examined in context with respirometric tests and abiotic parameters. Respiration activity reflected well the process stage, verifying the value of respirometric tests to access compost stability. SOUR values below 1 mg O(2)/g VS/h were achieved for the PM and the GW compost.

Microbial characterization during composting of biowaste.

Windrow composting of source-separated biowaste was studied in a pilot plant in Crete, with regard to abiotic factors, gas concentration in the pile and succession of functional microbial groups. The pH, C/N ratio and VS content, as well as the O(2) and CO(2) concentration, correlated well with composting time, indicating typical composting behaviour. Most of the microbial groups examined exhibited their highest counts towards the end of the thermophilic phase, with declining trends thereafter. The population of total mesophilic and thermophilic bacteria increased during the mild thermophilic phase and followed the temperature decline thereafter. Results on these microbial groups and fungi indicate that the timing of the thermophilic stage in the composting process, in addition to the peak temperature and duration of the stage, affects the microbial succession. Escherichia coli were detected for over 2 months of processing, in spite of the high temperatures achieved; only after about 3 months of composting did its population decline below the detection limit.

Methane and carbon dioxide emission in a two-phase olive oil mill sludge windrow pile during composting.

The aim of this work was to make some preliminary evaluations on CO(2) and CH(4) emissions during composting of two-phase olive oil mill sludge (OOMS). OOMS, olive tree leaves (OTL) and shredded olive tree branches (OTB) were used as feedstock for Pile I and Pile II with a 1:1:1 and 1:1:2v/v ratio, respectively. Each pile was originally 1.2m high, 2.0m wide and approximately 15.0m long. Four 500 ml volume glass funnels were inverted and introduced in each pile, two in the core (buried 50-60 cm from the surface) and two near the surface under a thin 10-15 cm layer of the mixture. Thin (0.5 cm diameter) plastic, 80 cm long tubes were connected to the funnels. A mobile gas analyser (GA2000) was used to measure the composition (by volume) of O2, CO2 and CH4 on a daily basis. The funnels were removed prior to each turning and reinserted afterwards. From each pair of funnels (core and surface) of both piles, one was kept closed between samplings. Two way ANOVA was used to test differences between piles and among the tubes. Post hoc Tukey tests were also used to further investigate these differences. There was a significant difference (at p<0.001) in the two piles for all three gases. The average concentrations of O2, CO2 and CH4 in Pile I, from all four funnels was 16.86%, 3.89% and 0.25%, respectively, where for Pile II the average values were 18.07%, 2.38% and 0.04%, respectively. The presence of OOMS in larger amounts in Pile I (resulting in more intense decomposing phenomena), and the larger particle size of OTB in Pile II (resulting in increasing porosity) are the probable causes of these significant differences. Samples from open funnels presented lower, but not significantly lower, O2 composition (higher for CO2 and CH4) in comparison with closed funnels in both depths and both piles. Not significant were also the different mean gas compositions between core and surface funnels in the same pile.

Heavy metals fractionation during the thermophilic phase of sewage sludge composting in aerated static piles.

An aerated static pile system with temperature feedback control was used for the composting of sewage sludge amended with olive tree leaves in a 1:1 (SS1) and 1:2 (SS2) v/v ratio, on two different occasions. The two piles were approximate 20 m3 each of similar dimensions; 2.0 wide at the base, 1.3 m height and 11 m long. Samples were taken from the core of the piles on four occasions: day 0 (establishment), day 15, day 30 and day 60 of the thermophilic phase. Heavy metal (Cu, Ni, Pb and Zn) fractions in each of the samples were monitored using sequential extraction with H2O (for the water soluble fraction), KCL (for the exchangeable fraction), Na2EDTA (for the inorganic bound fraction), NaOH (for the organically bound fraction) and HNO3 due the significant residual fraction of these metals in both piles and in all four samplings, which reduced any losses through leaching when water was added. For Ni the water soluble and the exchangeable fractions were dominant, reaching values of 45% in SS1 and 35% in SS2, resulting in some losses into the leachates. The fraction of metals connected to the organic matter was similar for Ni in both piles, larger in SS2 for Pb than in SS1, whereas Cu and Zn presented far larger values in SS1 than in SS2. There was no common pattern of fractionation variation among the metals in each pile or when comparing both piles.

Efforts to explain and control the prolonged thermophilic period in two-phase olive oil mill sludge composting.

The aim of this paper was to evaluate the use of different bulking agents in different ratios as a means to control, optimise and eventually reduce the duration of the thermophilic period in two-phase olive oil mill sludge (OOMS) composting. The bulking agents used were: (i) olive tree leaves (OTL), (ii) olive tree shredded branches (OTB) and (iii) woodchips (WDC). The selection of these materials was based on their abundance and availability on the island of Crete, the southernmost point of Greece. The ratios studied were: Pile 1, OOMS:OTL in 1:1 v/v; Pile 2, OOMS:WDC in 1:1.5 v/v; Pile 3, OOMS:OTL in 1:2 v/v; Pile 4, OOMS:OTL:OTB in 1:1:1 v/v; and Pile 5, OOMS:OTL:OTB in 1:1:2 v/v. The composting system used was that of windrows with the volume of each pile approximately 20-25 m3. The experiments took place over two consecutive years. A composting turner was used and turnings were performed at one and two week intervals. In each pile a variety of physiochemical parameters were monitored. Temperature remained high in all five trials. Piles 1, 2, 3, 4 and 5 temperatures recorded values of above 50 degrees C for 106, 158, 160, 175 and 183 days, respectively. Volumes were reduced by approximately 67%, 62%, 63%, 80% and 84%, respectively. Temperature remained high, mainly due to the presence in large amounts of oily substances which during their complete oxidation release important amounts of energy and aid the cometabolism of more stable molecules such as lignin. This process is better described as the slow "burning" of a "fuel" mixture in an "engine" than composting. This approach is based on the extensive similarities of this process to that of crude oil sludge or similar waste composting.

Treatment of olive mill effluents by coagulation-flocculation-hydrogen peroxide oxidation and effect on phytotoxicity.

The pre-treatment of olive mill effluents (OME) by means of coagulation-flocculation coupling various inorganic materials and organic poly-electrolytes was investigated. Tests were conducted with two different OME with chemical oxygen demand (COD) contents of 61.1 and 29.3 g/L, total suspended solids (TSS) of 36.7 and 52.7 g/L and total phenolic contents (TP) of 3.5 and 2.5 g/L, respectively. Inorganic materials such as lime, iron, magnesium and aluminum as well as four cationic and two anionic commercial poly-electrolytes were employed either alone or in various combinations and screened with respect to their efficiency in terms of TSS, TP and COD removal, the amount of sludge produced and the phytotoxicity of the resulting liquid to lettuce seeds. Coupling lime or ferrous sulphate (in the range of several g/L) with cationic poly-electrolytes (in the range of 200-300 mg/L) led to quantitative TSS removal, while COD and TP removal varied between about 10-40% and 30-80%, respectively, depending on the materials and the effluent in question; separation efficiency generally decreased with decreasing coagulant and/or flocculant concentration. To enhance organic matter degradation, iron-based coagulation was coupled with H(2)O(2), thus simulating a Fenton reaction and this increased COD reduction to about 60%. The original, untreated OME was strongly phytotoxic to lettuce seeds even after several dilutions with water; however, phytotoxicity decreased considerably following treatment with lime and cationic poly-electrolytes; this was attributed to the removal of phenols and other phytotoxic species from the liquid phase.

Sanitary aspect of using partially treated landfill leachate as a water source in green waste composting.

Shredded green wastes were composted in windrows, at the Harewood Whin landfill, near the city of York, in West Yorkshire, UK. Landfill leachate were added twice during the second and fourth week of the process in two piles. One pile was turned once every week for eight weeks and the other was turned twice, during the same period. Each time approximately, 2 m3 of leachate was added, into each pile. The two piles each contained about 45 m3 of shredded green waste. The effect of adding leachate on the sanitisation of the green waste during composting, was evaluated based on the changes in the levels of faecal coliforms and faecal streptococci. The results suggested that using leachate as the moisture source had no significant effect (tested with two factors ANOVA test) on the sanitisation process when compared with two similar piles, used as the control, for which tap water was used for moisture addition. In all four piles sanitisation was almost complete and below the acceptable levels. Additionally, the results indicated that there was no significant effect on the sanitisation process of the turning frequency.

The removal of NH3-N from primary treated wastewater in subsurface reed beds using different substrates.

Subsurface flow experimental reed beds, were designed and built based on a combination of two design methodologies, that of the WRc and Severn Trent Water plc (3) and that of the USA, EPA (17). Four different growing media were used with a combination of top soil, gravel, river sand and mature sewage sludge compost, aiming to determine the best substrate for ammonia removal. Eight units were constructed, two for each material. One bed for each pair was planted with Typha latifolia plants commonly known as cattails. Primary treated domestic wastewater, was continuously fed in to the bed for more than six months. The best results were achieved by the gravel reed beds with an almost constant removal rate of NH3-N above 80%. There was no significance difference on the performance of planted and unplanted reed beds.