A Low-Cost Ecofriendly Oxidation Process to Manufacture High-Performance Polymeric Biosurfactants Derived from Municipal Biowaste.

Biosurfactants account for about 12% of the global value of the surfactant market, which is currently dominated by synthetic surfactants obtained from fossil sources. Yet, the production of biosurfactants from renewable feedstock is bound to increase, driven by the increasing pressure from both society and governments for chemistry-based industries to become more ecofriendly and economically sustainable. A photo-chemical oxidation process is reported here, yielding new biosurfactants from urban biowaste in water that perform as a solvent and terminal oxidant reagent at room temperature without the addition of conventional oxidants and catalysts. Products with 200-500 kDa molecular weight are obtained. They lower the surface tension of water down to 34 mN/m at 0.5-2 g/L concentration. The estimated cost is rather low (0.1-1.5 EUR/kg), which is competitive with the cost of synthetic surfactants but much lower than the cost of the best-performing bacterial surfactants. For the implementation of the photo-chemical oxidation process at the industrial level, the results suggest that the new biosurfactants obtained in the present work may not reach the performance level of the best-performing bacterial surfactants capable of lowering the surface tension of water down to 28 mN/m. Yet, the biosurfactants produced by the photo-chemical process have a greater chance of being marketed on large scales.

Enhancing Lettuce Yield through Innovative Foliar Spray of Biopolymers Derived from Municipal Biowastes.

Municipal waste biomass could be valorized as an alternative feedstock to produce compounds beneficial for agricultural applications. The foliar spray application of biostimulants emerges as a promising and innovative technique due to its environmental safety and ability to enhance crop yields. In recent years, the exploitation of biopolymers obtained through alkaline hydrolysis of the solid anaerobic digestate from municipal biowastes has attracted researchers' interest. The aim of this study is to investigate the effects on lettuce growth of a product obtained through alkaline hydrolysis from municipal biowaste, Biopolymers (BPs), and of a derivate subjected to a further oxidation process, Biopolymers Oxidate (BPs OX). The effects of the treatments at various concentrations were evaluated by monitoring plant growth and observing the trends in the activities of the main enzymes involved in the nitrogen metabolic pathway of lettuce. Results suggest that the best treatments in terms of fresh weight were achieved by using BPs at 10 mg/L and BPs OX at 100 mg/L, increasing yield by around 28% and 34%, respectively. The innovative aspect of this work was to make easier for farmers the biopolymers application by testing a foliar spray methodology for BPs and BPs OX, which has never been tested before in any crop.

The Autocatalytic Chemical Reaction of a Soluble Biopolymer Derived from Municipal Biowaste.

The paper discusses the perspectives of further implementation of the autocatalytic properties of a soluble biopolymer (SBP) derived from municipal biowastes for the realisation of a biorefinery producing value-added bio-products for consumer use. The reaction of an SBP and water is reported to cause the depolymerisation and oxidation of the pristine SBP organic matter with the formation of carboxyl-functionalised polymers having lower molecular weight and CO2. These findings demonstrate the oxidation of the SBP via water, which could only occur through the production of O and OH radicals catalysed by the SBP. According to the adopted experimental plan, the anaerobic digestate supplied by an Italian municipal biowaste treatment plant was hydrolysed in pH 13 water at 60 °C. The dry product was re-dissolved in plain water at pH 10 and used as a control against the same solution with hydrogen peroxide at 0.1-3 H2O2 moles per SBP carbon mole added. The control and test solutions were kept at room temperature, in the dark or in a climatic chamber under irradiation with simulated solar light, until the pH of the solutions remained constant. Afterwards, the solutions were processed to recover and analyse the crude soluble products. The present work reports the results obtained for the control solution and for the test solutions treated in the presence and absence of H2O2, with and without pH control, in the dark and under irradiation with simulated solar light.

Mild Chemical Treatment of Unsorted Urban Food Wastes.

Municipal biowastes are conventionally treated by assessed anaerobic and aerobic fermentation to produce biogas, anaerobic digestate, and compost. Low-temperature hydrolysis and the oxidation of the digestate and compost, which are still at the experimental stage, are known to yield water-soluble value-added chemical specialities for use in different sectors of the chemical industry and in agriculture. The present paper reports the application of the two chemical reactions to the biowastes before fermentation. The products obtained in this manner are compared with those obtained from the chemical reactions applied to the fermented biowastes. Based on the experimental results, the paper discusses the expected environmental and economic benefits of the above chemical processes and products in comparison with the products obtained by other known biotechnologies for the valorisation of biomass as a feedstock for the biobased chemical industry. The results point out that a sustainable biowaste-based refinery that produces biofuel and biobased chemicals may be developed by integrating chemical and fermentation technologies.

Effect of municipal biowaste derived biostimulant on nitrogen fate in the plant-soil system during lettuce cultivation.

A main concern of agriculture is to improve plant nutrient efficiency to enhance crop yield and quality, and at the same time to decrease the environmental impact caused by the lixiviation of excess N fertilizer application. The aim of this study was to evaluate the potential use of biopolymers (BPs), obtained by alkaline hydrolysis of the solid anaerobic digestate of municipal biowastes, in order to face up these main concerns of agriculture. The experimental trials involved the application of BPs (at 50 and 150 kg/ha) alone or mixed with different amounts (100%, 60% and 0%) of mineral fertilizer (MF). Three different controls were routinely included in the experimental trials (MF 100%, 60% and 0%). The effect of BPs on lettuce was evaluated by monitoring growth parameters (fresh and dry weights of shoot and root, nitrogen use efficiency), and the N-flux in plant-soil system, taking into account the nitrate leached due to over irrigation events. The activities of enzymes involved in the nitrogen uptake (nitrate reductase, glutamate synthase and glutamine synthase), and the nitrogen form accumulated in the plant tissues (total N, protein and NO3-) were evaluated. The results show that the application to the soil of 150 kg/ha BPs allows to increase lettuce growth and nitrogen use efficiency, trough stimulation of N-metabolism and accumulation of proteins, and hence to reduce the use of MF by 40%, thus decreasing the nitrate leaching. These findings suggest that the use of BPs as biostimulant greatly contributes to reduce the consumption of mineral fertilizers, and to mitigate the environmental impact caused by nutrients leaching, according to European common agricultural policy, that encourages R&D of new bioproducts for sustainable eco-friendly agriculture.

Processed vs. non-processed biowastes for agriculture: effects of post-harvest tomato plants and biochar on radish growth, chlorophyll content and protein production.

The aim of this work was to address the issue of processed vs. non-processed biowastes for agriculture, by comparing materials widely differing for the amount of process energy consumption. Thus, residual post harvest tomato plants (TP), the TP hydrolysates obtained at pH 13 and 60 °C, and two known biochar products obtained by 650 °C pyrolysis were prepared. All products were characterized and used in a cultivation of radish plants. The chemical composition and molecular nature of the materials was investigated by solid state 13C NMR spectrometry, elemental analysis and potentiometric titration. The plants were analysed for growth and content of chlorophyll, carotenoids and soluble proteins. The results show that the TP and the alkaline hydrolysates contain lignin, hemicellulose, protein, peptide and/or amino acids moieties, and several mineral elements. The biochar samples contain also similar mineral elements, but the organic fraction is characterized mainly by fused aromatic rings. All materials had a positive effect on radish growth, mainly on the diameter of roots. The best performances in terms of plant growth were given by miscanthus originated biochar and TP. The most significant effect was the enhancement of soluble protein content in the plants treated with the lowest energy consumption non processed TP. The significance of these findings for agriculture and the environment is discussed.

Chemical modeling of acid-base properties of soluble biopolymers derived from municipal waste treatment materials.

This work reports a study of the proton-binding capacity of biopolymers obtained from different materials supplied by a municipal biowaste treatment plant located in Northern Italy. One material was the anaerobic fermentation digestate of the urban wastes organic humid fraction. The others were the compost of home and public gardening residues and the compost of the mix of the above residues, digestate and sewage sludge. These materials were hydrolyzed under alkaline conditions to yield the biopolymers by saponification. The biopolymers were characterized by 13C NMR spectroscopy, elemental analysis and potentiometric titration. The titration data were elaborated to attain chemical models for interpretation of the proton-binding capacity of the biopolymers obtaining the acidic sites concentrations and their protonation constants. The results obtained with the models and by NMR spectroscopy were elaborated together in order to better characterize the nature of the macromolecules. The chemical nature of the biopolymers was found dependent upon the nature of the sourcing materials.

Benefits for agriculture and the environment from urban waste.

Soluble bio-based substances (SBO) that have been isolated from urban biowaste have recently been reported to enhance plant leaf chlorophyll content and growth. The same SBO have also been shown to enhance the photochemical degradation of organic pollutants in industrial effluent. These findings suggest that SBO may promote either C fixation or mineralization, according to operating conditions. The present work aims to investigate SBO performance, as a function of source material. Thus, three materials have been sampled from a municipal waste treatment plant: (i) the digestate of the anaerobic fermentation of a humid organic fraction, (ii) a whole vegetable compost made from gardening residues and (iii) compost made from a mixture of digestate, gardening residues and sewage sludge. These materials were hydrolyzed at pH13 and 60°C to yield SBO that display different chemical compositions. These products were applied to soil at 30, 145 and 500 kg ha(-1) doses for tomato cultivation. Soil and plant leaf chemical composition, plant growth, leaf chlorophyll content and CO2 exchange rate as well as fruit quality and production rate were measured. Although it did not affect the soil's chemical composition, SBO were found to significantly increase plant photosynthetic activity, growth and productivity up to the maximum value achieved at 145 kg ha(-1). The effects were analyzed as a function of SBO chemical composition and applied dose. The results of this work, compared with those of previous works, indicate that urban biowaste, if properly exploited, may furnish conjugate economic and environmental benefits, within a friendly sustainable ecosystem.

Paramagnetic iron-doped hydroxyapatite nanoparticles with improved metal sorption properties. A bioorganic substrates-mediated synthesis.

This paper describes the synthesis of paramegnetic iron-containing hydroxyapatite nanoparticles and their increased Cu(2+) sorbent capacity when using Ca(2+) complexes of soluble bioorganic substrates from urban wastes as synthesis precursors. A thorough characterization of the particles by TEM, XRD, FTIR spectroscopy, specific surface area, TGA, XPS, and DLS indicates that loss of crystallinity, a higher specific area, an increased surface oxygen content, and formation of surface iron phases strongly enhance Cu(2+) adsorption capacity of hydroxyapatite-based materials. However, the major effect of the surface and morphologycal modifications is the size diminution of the aggregates formed in aqueous solutions leading to an increased effective surface available for Cu(2+) adsorption. Maximum sorption values of 550-850 mg Cu(2+) per gram of particles suspended in an aqueous solution at pH 7 were determined, almost 10 times the maximum values observed for hydroxyapatite nanoparticles suspensions under the same conditions.

Refuse derived soluble bio-organics enhancing tomato plant growth and productivity.

Municipal bio-refuse (CVD), containing kitchen wastes, home gardening residues and public park trimmings, was treated with alkali to yield a soluble bio-organic fraction (SBO) and an insoluble residue. These materials were characterized using elemental analysis, potentiometric titration, and 13C NMR spectroscopy, and then applied as organic fertilizers to soil for tomato greenhouse cultivation. Their performance was compared with a commercial product obtained from animal residues. Plant growth, fruit yield and quality, and soil and leaf chemical composition were the selected performance indicators. The SBO exhibited the best performance by enhancing leaf chlorophyll content, improving plant growth and fruit ripening rate and yield. No product performance-chemical composition relationship could be assessed. Solubility could be one reason for the superior performance of SBO as a tomato growth promoter. The enhancement of leaf chlorophyll content is discussed to identify a possible link with the SBO photosensitizing properties that have been demonstrated in other work, and thus with photosynthetic performance.

Waste-derived bioorganic substances for light-induced generation of reactive oxygenated species.

Urban waste-derived bioorganic substances (UW-BOS) have shown promise as chemical auxiliaries for a number of technological applications in the chemical industry and in environmental remediation. In this study, the application of these substances in the photodegradation of organic pollutants is addressed. The experimental work is specifically focused on the photolysis mechanism promoted by AC8, a UW-BOS isolated from a 2:1 w/w mixture of food and green residues, composted for 110 days, using 4-chlorophenol (4-CP) as probe molecule. The production of (⋅)OH and the ¹O2 is monitored by EPR spectroscopy. The correlation between radical species evolution and photodegradation of 4-CP is investigated. The effect of ¹O2 and (⋅)OH scavengers on the 4-CP degradation process is also checked. The results suggest that the role of these species in the photodegradation of 4-CP depends on AC8 concentration. AC8 is thereby proven to be a photosensitizer for applications in environmental remediation. The results on AC8 further support the use of urban bio-waste as a versatile source of chemical auxiliaries of biological origin for use in diversified applications.

Acid soluble bio-organic substances isolated from urban bio-waste. Chemical composition and properties of products.

As previous work proposed commercial expectations for soluble bio-organic substances (SBO) isolated from compost of urban food, gardening and park trimming residues as chemical auxiliaries, nine urban bio-wastes (BW) treated by aerobic and anaerobic digestion for 0-360 days were used to extract SBO and investigate source variability effects on product chemical composition and properties. The bio-wastes were collected over a 13732 km(2) area populated by 2.9 millions from 565 municipalities. The SBO were characterized by their content of different C types and functional groups and by their distribution coefficient (K(PEGW)) between polyethylene glycol and water. A significant linear correlation was found between K(PEGW) and the lipophilic/hydrophilic C ratio. The investigated SBO exhibited up to sixfold change of K(PEGW) demonstrating that BW available from densely populated urban areas are an interesting exploitable source of a wide variety of potential products for the chemical market.

Behavior and properties in aqueous solution of biopolymers isolated from urban refuse.

Acid soluble biopolymeric substances (SBP) were isolated from different urban biowastes comprised of a range of materials available from metropolitan areas. These biowastes provided products with a chemical nature and solubility properties changing over a wide range and, thus, allowed to assess the effect of the variability of the chemical nature on molecular conformation and surface activity in water solution. For this scope, the SBP were characterized for chemical composition and molecular weight (MW) by microanalysis, potentiometric titration, (13)C NMR spectroscopy, and size exclusion chromatography (SEC) coupled with an online multiangle light scattering (MALS) detector. These materials were found to have 67-463 kg mol(-1) MW and 6-53 polydispersity index and to contain carboxylic acid and phenol groups bonded to aromatic and aliphatic C chains. An empirical parameter (LH) was calculated for use as an index of the lipophilic/hydrophilic C atoms ratio. The products solubility properties in solvents of different polarity, surface activity, power to enhance the water solubility of hydrophobic compounds, and particle size in water solution were also investigated by measurements of the products partition coefficient between polyethylene glycol and water (KPEGW) and of air-water surface tension (γ), water-hexane interfacial tension (IFT), disperse red orange dye solubility (DS), and dynamic light scattering (DLS) versus added SBP concentration (Cs). The results indicate that LH correlates well with KPEGW and with the products surface activity properties. Both γ and DS are shown to depend on Cs, although in opposite ways, that is, higher Cs values yield lower γ and higher DS values. Both DS-Cs and γ-Cs plots showed a significant slope change at approximately the same 1.8-2.5 g L(-1) Cs value. This suggested a change of molecular conformation taking place at the above Cs values. Hydrodynamic diameter values for SBP in solution at Cs ≤ 10 g L(-1) were found to range from 130 to 300 nm, consistent with their macromolecular nature. The DLS coupled to the γ data were consistent with molecules at the water-air interphase and in the bulk water phase having different conformations, but not significantly different molecular sizes. Molecular aggregates more likely form at 50-100 g L(-1) Cs. The results confirm that urban biowastes are a sustainable source of biobased products that may have real commercial perspectives.

A waste-derived biosurfactant for the preparation of templated silica powders.

A polymeric anionic biosurfactant isolated from urban bio-wastes was used as a template for fabricating silica powders of pore size ranging from 4 to 30 nm by the sol-gel reaction of tetraethylorthosilicate and 3-aminopropyltriethoxysilane at pH 5. The morphology of the synthesized silica powders was found to depend on the size and the conformation of the biosurfactant molecules or aggregates in solution. The use of waste-derived biosurfactants as templating agents reduces the fabrication costs and the environmental impact of mesoporous materials. At the same time, it encourages the upgrade of bio-wastes from a costly disposal matter to a source of chemicals and therefore, of revenue.

Biosurfactants from urban green waste.

From waste came forth surfactants: Humic acid like substances isolated from 0-60 day-old compost display excellent surface activity and solvent properties. These biosurfactants were used to solubilize a dye in water below and above their critical micellar concentration. The biosurfactant unimers appear to have higher dye-solubilizing power than the corresponding micelles.Humic acid like substances isolated from compost show potential as chemical auxiliaries. In the present study, three surfactant samples were obtained from green waste composted for 0-60 days to assess aging effects of the source on the properties of the products. The surface activity, dye solubility enhancement, and chemical nature of these substances were compared. No differences in performance were established among the samples. They lower water surface tension and enhance the dye solubility upon increasing their concentration. However, the ratio of soluble dye to added surfactant is higher in the premicellar than in the postmicellar concentration region. Structural investigations indicated the humic acid like substances to be amphiphiles with molecular weights in the range of 1-3 x 10(5) g mol(-1). The surfactant samples were also compared to sodium dodecylbenzenesulfonate, polyacrylic acid, and soil and water humic substances. The results encourage the application of compost as a source of low-cost biosurfactant.

Use of biosurfactants from urban wastes compost in textile dyeing and soil remediation.

A compost isolated humic acid-like (cHAL) material was pointed out in previous work for its potential as auxiliary in chemical technology. Its potential is based on its relatively low 0.4gL(-1) critical micellar concentration (cmc) in water, which enables cHAL to enhance the water solubility of hydrophobic substances, like phenanthrene, when used at higher concentrations than 0.4gL(-1). This material could be obtained from a 1:1 v/v mixture of municipal solid and lignocellulosic wastes composted for 15 days. The compost, containing 69.3% volatile solids, 39.6% total organic C and 21C/N ratio, was extracted for 24h at 65 degrees C under N2 with aqueous 0.1molL(-1) NaOH and 0.1molL(-1) Na4P2O7, and the solution was acidified to separate the precipitated cHAL in 12% yield from soluble carbohydrates and other humic and non-humic substances. In this work two typical applications of surfactants, i.e., textile dyeing (TD) and soil remediation by washing (SW), were chosen as grounds for testing the performance of the cHAL biosurfactant against the one of sodium dodecylsulfate (SDS), which is a well established commercial synthetic surfactant. The TD trials were carried out with nylon 6 microfiber and a water insoluble dye, while the SW tests were performed with two soils contaminated by polycyclic aromatic hydrocarbons (PAH) for several decades. Performances were rated in the TD experiments based on the fabric colour intensity (DeltaE) and uniformity (sigmaDeltaE), and in the SW experiments based on the total hydrocarbons concentration (CWPAH) and on the residual surfactant (Cre) concentrations in the washing solution equilibrated with the contaminated soils. The results show that both cHAL and SDS exhibit enhanced performance when applied above their cmc values. However, while in the TD case a significant performance effect was observed at the surfactants cmc value, in the SW case the required surfactants concentration values were equivalent to 25-125xcmc for cHAL and to 4-22xcmc for SDS. The vis-a-vis comparison of the two surfactants gave the following results: in the TD case the cHAL biosurfactant at 0.4gL(-1) yields good colour intensity and equal colour uniformity as SDS at 5gL(-1), in the SW case cHAL was found to enhance CWPAH by a factor of 2-4 relative to SDS with one soil, whereas with the other soil the two surfactants behaved similarly. The Cre data, however, showed that both soils absorbed by far more SDS (68-95%) than cHAL (12-54%). The results point out intriguing technological and environmental perspectives deriving from the use of compost isolated biosurfactants in the place of synthetic surfactants.

Modification of soil humic matter after 4 years of compost application.

Two soil plots, 1 ha each, were amended yearly for 4 years, respectively, with 35.8 and 71.6 Mg ha(-1) yr(-1) of mature compost (CM) obtained from food and vegetable residues. The compost, amended soils, and a control soil plot after 4 years (S4), were analyzed for humin (HUC), humic acid (HAC), fulvic acid (FAC), and non-humic carbon (NHC) content. Compared to S4, the amended soil contained more humified C (HAC, FAC and HUC) and less NHC. Further evidence of the effect of compost on soil organic matter was obtained by the analysis of the humic acid (HA) fractions isolated from both the compost and the soils. These were characterized by elemental analyses and Diffuse Reflectance Infrared Fourier Transformed spectroscopy. The HAs isolated from CM and from S4 were significantly different. The HAs isolated from the amended plots were more similar to HA isolated from CM than to HA isolated from S4. The experimental data of this work indicate that the compost application may affect significantly the soil organic matter composition, and that the approach used in this work allows one to trace the fate of compost organic matter in soil.

Compost effect on soil humic acid: A NMR study.

The humic acid (HA) fraction of a food and vegetable residues compost (CM) was taken as indicator to trace the fate of CM organic matter in four years CM amended soil. (1)H and (13)C NMR spectroscopy were used to investigate the nature of the HA isolates from CM, control soil (S(4)) and amended soil. The result indicated a significant structural difference between CM HA and S(4) HA, and supported the presence of both HA fractions in soil at the end of the amendment trials. However, the nature and content of CM HA in soil did not fully explain the increase of soil cation exchange capacity (CEC) after amendment. All CM humic fractions (i.e., fulvic acid, humic acid and humin) were found to contribute to the change of the soil organic matter composition. It is concluded that although CM HA is a suitable indicator of the survival of compost organic matter in soil during amendment, all three humic fractions should be monitored and analyzed to fully understand changes in the composition and properties of amended soil.

Chemicals from wastes: compost-derived humic acid-like matter as surfactant.

Compost humic acid-like (cHAL) polymeric matter (MW = 15610), isolated in 12% yield from food and green waste compost, exhibits very good surfactant properties in aqueous solution: i.e., critical micelle concentration (cmc) = 403 mg/L and surface tension at cmc = 36.1 mN/m. Values of cmc are confirmed also by conductivity and phenanthrene solubility measurements. These results, compared with those for other major commercial and research surfactants, propose cHAL as a competitive low-cost biosurfactant.