Methane potential of fruit and vegetable waste: an evaluation of the semi-continuous anaerobic mono-digestion.

The anaerobic digestion (AD) of a high diversity blend of fruit and vegetable waste (FVW) generated in tropical conditions as a single substrate was performed. A continuously stirred tank reactor (CSTR) operated in semi-continuous regime was used for AD. The reactor performance was monitored with gradually increasing organic loading rates (OLRs) from 0.5 up to 5.0 gVS L-1 d-1. The biochemical methane potential (BMP) of FVW determined by batch bottles was 360 LN CH4 kgVS-1, with a biodegradability of 79%. A stable pH with an adequate level of buffering capacity was observed during the entire experiment. Methane yield indicated the best performance at an OLR of 3.0 gVS L-1 d-1, with 285 LN CH4 kgVS-1 added, reaching 79% of BMP. At an OLR over 3.0 gVS L-1 d-1 accumulation of volatile fatty acids (VFA) was detected; in particular, propionic acid was monitored, and a decreased methane yield was detected. Biogas production rate was 1.55 LN L-1 d-1 and showed linear increase according to increases in the OLR.

Influence of chemical composition on biochemical methane potential of fruit and vegetable waste.

This study investigates the influence of chemical composition on the biochemical methane potential (BMP) of twelve different batches of fruit and vegetable waste (FVW) with different compositions collected over one year. BMP ranged from 288 to 516LNCH4kgVS-1, with significant statistical differences between means, which was explained by variations in the chemical composition over time. BMP was most strongly correlated to lipid content and high calorific values. Multiple linear regression was performed to develop statistical models to more rapidly predict methane potential. Models were analysed that considered chemical compounds and that considered only high calorific value as a single parameter. The best BMP prediction was obtained using the statistical model that included lipid, protein, cellulose, lignin, and high calorific value (HCV), with R2 of 92.5%; lignin was negatively correlated to methane production. Because HCV and lipids are strongly correlated, and because HCV can be determined more rapidly than overall chemical composition, HCV may be useful for predicting BMP.

Optimization of the anaerobic co-digestion of pasteurized slaughterhouse waste, pig slurry and glycerine.

The feasibility of co-digestion of blends of two different animal by-products (pig manure and pasteurized slaughterhouse waste) and recovered glycerine was studied in mesophilic conditions. Experiments were performed in a lab-scale CSTR along 490days, with a hydraulic retention time of 21-33days and with a step-wise increased organic loading rate, by adding and/or changing the wastes ratio, from 0.8 to 3.2kgCODm-3d-1. The best methane production rate (0.64Nm3CH4m-3d-1) represented an increment of 2.9-fold the initial one (0.22Nm3CH4m-3d-1 with pig manure solely). It was attained with a ternary mixture composed, in terms of inlet volatile solids, by 35% pig slurry, 47% pasteurized slaughterhouse waste and 18% glycerine. This blend was obtained through a stepwise C/N adjustment: this strategy led to a more balanced biodegradation due to unstressed bacterial populations through the performance, showed by the VFA-related indicators. Besides this, an improved methane yield (+153%) and an organic matter removal efficiency (+83%), regarding the digestion of solely pig slurry, were attained when the C/N ratio was adjusted to 10.3.

Assessment of different pre-treatment methods for the removal of limonene in citrus waste and their effect on methane potential and methane production rate.

The objective of this study was to assess the limonene removal efficiency of three pre-treatment methods when applied to citrus waste and to evaluate their effects on the biochemical methane potential and the methane production rate using batch anaerobic tests. The methods tested were based on removal (biological pretreatment by fungi) or recovery (steam distillation and ethanol extraction) of limonene. All the treatments decreased the concentration of limonene in orange peel, with average efficiencies of 22%, 44% and 100% for the biological treatment, steam distillation and ethanol extraction, respectively. By-products from limonene biodegradation by fungi exhibited an inhibitory effect also, not making interesting the biological pretreatment. The methane potential and production rate of the treated orange peel increased significantly after applying the recovery strategies, which separated and recovered simultaneously other inhibitory components of the citrus essential oil. Apart from the high recovery efficiency of the ethanol extraction process, it presented a favourable energy balance.

Assessment of groundwater vulnerability to nitrates from agricultural sources using a GIS-compatible logic multicriteria model.

In the present study an overlay method to assess groundwater vulnerability is proposed. This new method based on multicriteria decision analysis (MCDA) was developed and validated using an appropriate case study in Aragon area (NE Spain). The Vulnerability Index to Nitrates from Agricultural Sources (VINAS) incorporates a novel Logic Scoring of Preferences (LSP) approach, and it has been developed using public geographic information from the European Union. VINAS-LSP identifies areas with five categories of vulnerability, taking into account the hydrogeological and environmental characteristics of the territory as a whole. The resulting LSP map is a regional screening tool that can provide guidance on the potential risk of nitrate pollution, as well as highlight areas where specific research and farming planning policies are required.

Estimation of parameter uncertainty for an activated sludge model using Bayesian inference: a comparison with the frequentist method.

The procedure commonly used for the assessment of the parameters included in activated sludge models (ASMs) relies on the estimation of their optimal value within a confidence region (i.e. frequentist inference). Once optimal values are estimated, parameter uncertainty is computed through the covariance matrix. However, alternative approaches based on the consideration of the model parameters as probability distributions (i.e. Bayesian inference), may be of interest. The aim of this work is to apply (and compare) both Bayesian and frequentist inference methods when assessing uncertainty for an ASM-type model, which considers intracellular storage and biomass growth, simultaneously. Practical identifiability was addressed exclusively considering respirometric profiles based on the oxygen uptake rate and with the aid of probabilistic global sensitivity analysis. Parameter uncertainty was thus estimated according to both the Bayesian and frequentist inferential procedures. Results were compared in order to evidence the strengths and weaknesses of both approaches. Since it was demonstrated that Bayesian inference could be reduced to a frequentist approach under particular hypotheses, the former can be considered as a more generalist methodology. Hence, the use of Bayesian inference is encouraged for tackling inferential issues in ASM environments.

Study of thermal pre-treatment on anaerobic digestion of slaughterhouse waste by TGA-MS and FTIR spectroscopy.

Thermogravimetric analysis coupled to mass spectrometry (TGA-MS) and Fourier-transform infrared spectroscopy (FTIR) were used to describe the effect of pasteurization as a hygienic pre-treatment of animal by-products over biogas production. Piggery and poultry meat wastes were used as substrates for assessing the anaerobic digestion under batch conditions at mesophilic range. Poultry waste was characterized by high protein and carbohydrate content, while piggery waste presented a major fraction of fat and lower carbohydrate content. Results from anaerobic digestion tests showed a lower methane yield for the pre-treated poultry sample. TGA-MS and FTIR spectroscopy allowed the qualitative identification of recalcitrant nitrogen-containing compounds in the pre-treated poultry sample, produced by Maillard reactions. In the case of piggery waste, the recalcitrant compounds were not detected and its biodegradability test reported higher methane yield and production rates. TGA-MS and FTIR spectroscopy were demonstrated to be useful tools for explaining results obtained by anaerobic biodegradability test and in describing the presence of inhibitory problems.

Multi-criteria analyses of wastewater treatment bio-processes under an uncertainty and a multiplicity of steady states.

This paper presents a multi-criteria evaluation methodology for determining the operating strategies for bio-chemical, wastewater treatment plants based on a model analysis under an uncertainty that can present multiple steady states. The method is based on Monte Carlo (MC) simulations and the expected utility theory in order to deal with the analysis of choices among risky operating strategies with multi-dimensional outcomes. The motivation is given by a case study using an anaerobic digestion model (ADM) adapted for multiple co-substrates. It is shown how the multi-criteria analyses' computational complexity can be reduced within an approximation based on Gaussian-process regression and how a reliability map can be built for a bio-process model under uncertainty and multiplicity. In our uncertainty-analyses case study, the reliability map shows the probability of a biogas-production collapse for a given set of substrates mixture input loads.

Determination of chemical oxygen demand in heterogeneous solid or semisolid samples using a novel method combining solid dilutions as a preparation step followed by optimized closed reflux and colorimetric measurement.

This paper reports the development of an innovative sample preparation method for the determination of the chemical oxygen demand (COD) in heterogeneous solid or semisolid samples, with high suspended solids and COD concentrations, using an optimized closed reflux colorimetric method. The novel method, named solid dilution (SD), is based on a different technique of sample preparation, diluting the sample with magnesium sulfate (MgSO(4)) previous to COD determination. With this, it is possible to obtain a solid homogeneous mixture much more easily analyzable. Besides, a modification of concentration and ratio of reagents was optimized to make the closed reflux colorimetric method suitable for complex substrates with COD levels ranging from 5 to 2500 g O(2) kg(-1) TS. The optimized method has been tested with potassium hydrogen phthalate (KHP) as primary solid standard and using different solid or semiliquid substrates like pig slaughterhouse waste and sewage sludge, among others. Finally, the optimized method (SD/SM-CRC) was intensively tested in comparison to the standard titrimetric method (SM-ORT) using different certified reference materials (CRM). The developed method was found to give higher accuracy, 1.4% relative standard deviation (RSD) vs 10.4%, and bias of 2.8% vs 8.0%, in comparison to the standard open reflux titrimetric method.

Empirical characterisation and mathematical modelling of settlement in composting batch reactors.

The settlement of organic matter during composting was measured at different levels during the active biodegradation phase in forced-aerated static reactors loaded with different mixtures of organic wastes. The temperature evolution and the concentration of oxygen and carbon dioxide were also recorded in the exhaust gases. Two two-parameter equations and their generalised three-parameter form were fitted to the experimental data and their capability to predict settlement as a function of time was discussed. The settlement field inside the reactors was successfully described with a linear profile. At any given time and vertical position, mass settlement was proportional to the initial height after reactor loading. Furthermore, a relationship linking settlement to biological activity was also proposed. Under all tested experimental conditions, settlement showed a clear correlation with the cumulative oxygen consumption that was modelled with a three parameter equation.

Mesophilic and thermophilic anaerobic biodegradability of water hyacinth pre-treated at 80 degrees C.

Water hyacinth (Eichornia crassipes) is a fast growing aquatic plant which causes environmental problems in continental water bodies. Harvesting and handling this plant becomes an issue, and focus has been put on the research of treatment alternatives. Amongst others, energy production through biomethanation has been proposed. The aim of this study was to assess the anaerobic biodegradability of water hyacinth under mesophilic and thermophilic conditions. The effect of a thermal sludge pre-treatment at 80 degrees C was also evaluated. To this end, anaerobic biodegradability tests were carried out at 35 degrees C and 55 degrees C, with raw and pre-treated water hyacinth. According to the results, the thermal pre-treatment enhanced the solubilisation of water hyacinth (i.e. increase in the soluble to total chemical oxygen demand (COD)) from 4% to 12% after 30 min. However, no significant effect was observed on the methane yields (150-190 L CH(4)/kg volatile solids). Initial methane production rates for thermophilic treatments were two fold those of mesophilic ones (6-6.5L vs. 3-3.5 L CH(4)/kg COD x day). Thus, higher methane production rates might be expected from thermophilic reactors working at short retention times. The study of longer low temperature pre-treatments or pre-treatments at elevated temperatures coupled to thermophilic reactors should be considered in the future.

Manure treatment technologies: on-farm versus centralized strategies. NE Spain as case study.

Manure treatment has become an issue of concern in many farms in order to adequate their productions to the requirements of available arable lands. Such processing should be considered in the framework of a nutrient management planning (NMP) designed under local conditionals and considering cultivable soils as the end-users. In this context, decision on individual or collective scale should not be regarded as a main objective per se since such election should result from the NMP study and design. This paper is aimed to review existing experiences on manure treatment in NE Spain (Catalonia), either at farm or large scale. Some common factors identified in the successful experiences described are the involvement of farmers, technology suppliers and related authorities; energy and fertilizers prices; and the existence of a NMP as a global framework for actuations. Economical factors affecting decision about management and treatment scale are influenced by the density and the intensity of farming in a given area, which favour centralized NMPs and allow optimizing logistics.

Influence of synthetic packing materials on the gas dispersion and biodegradation kinetics in fungal air biofilters.

The biodegradation of toluene was studied in two lab-scale air biofilters operated in parallel, packed respectively with perlite granules (PEG) and polyurethane foam cubes (PUC) and inoculated with the same toluene-degrading fungus. Differences on the material pore size, from micrometres in PEG to millimetres in PUC, were responsible for distinct biomass growth patterns. A compact biofilm was formed around PEG, being the interstitial spaces progressively filled with biomass. Microbial growth concentrated at the core of PUC and the excess of biomass was washed-off, remaining the gas pressure drop comparatively low. Air dispersion in the bed was characterised by tracer studies and modelled as a series of completely stirred tanks (CSTR). The obtained number of CSTR (n) in the PEG packing increased from 33 to 86 along with the applied gas flow (equivalent to empty bed retention times from 48 to 12 s) and with operation time (up to 6 months). In the PUC bed, n varied between 9 and 13, indicating that a stronger and steadier gas dispersion was achieved. Michaelis-Menten half saturation constant (km) estimates ranged 71-113 mg m(-3), depending on the experimental conditions, but such differences were not significant at a 95% confidence interval. The maximum volumetric elimination rate (rm) varied from 23 to 50 g m(-3) h(-1). Comparison between volumetric and biomass specific biodegradation activities indicated that toluene mass transfer was slower with PEG than with PUC as a consequence of a smaller biofilm surface and to the presence of larger zones of stagnant air.

An integrated biochemical and physical model for the composting process.

A dynamic model for the composting process has been developed, which integrates several biochemical and physical processes. Different microbial populations (mesophilic and thermophilic bacteria, actinomycetes and fungi) have been considered, each specialized in certain types of polymeric substrates (carbohydrates, proteins, lipids, hemicellulose, cellulose and lignin) and their hydrolysis products. Heat and mass transfer between the three phases of the system have been taken into account. The gas phase was considered to be composed by nitrogen, oxygen, carbon dioxide, ammonia and water vapour. Model computer simulations provided results that fitted satisfactory the experimental data. A sensitivity analysis was performed to determine the key parameters of the model. The partition of both the composting mass and the active biomass into different major groups of substrates and specialized microbial populations, as well as the factors affecting the gas-liquid equilibrium, were important for an accurate description of the composting process.

Changes in the chemical and physicochemical properties of the solid fraction of cattle slurry during composting using different aeration strategies.

Replacement of peat as a growing medium by a renewable material, such as an organic waste, is an issue of concern since harvesting of peat has a considerable environmental impact and, actually, it is a non-renewable resource. Cattle manure is a readily available organic waste, which means that once it goes through the composting process, it can be used as an alternative to peat, specifically, the solid fraction obtained from mechanical liquid-solid separation of cattle slurry (SF). Studies have shown it to be suitable for such uses. The purpose of this study was to detect possible changes in the physicochemical and chemical properties of SF when it is composted using different aeration strategies, with an emphasis on the changes that would make it feasible for use as a substrate. With this aim in mind, an experiment was designed with three aeration strategies that would be used during composting. The first consisted of applying air through a static method (forced ventilation). The second involved improving aeration by adding a bulking agent and a dynamic turning method. In the third strategy, aeration was carried out by turning (control). The results show that the different aeration strategies had a clear effect on the evolution of pH, electrical conductivity (EC), nitrate-N, ammonia-N and bicarbonate content. Nitrification was favored under good aeration conditions using the static composting method, probably due to the greater availability of ammonia-N that was transformed into nitrate-N. In general, the low buffering capacity allowed for a reduction of the pH during the curing stage of composting (in conjunction with low temperatures during this period), a characteristic that favors the use of this compost as a growing medium. We also conclude that measuring bicarbonate levels during composting could be used as an indicator of the possible acidification of the material and as a way of evaluating the level of material aeration.

Dynamic simulation of pH in anaerobic processes.

With the objective of contributing to the buildup of mathematical tools for anaerobic process simulation, an algorithm for the dynamic simulation of pH was developed. The dynamic simulation of the gaseous phase variables was also considered. The pH algorithm was validated for a watery system, obtaining good agreement between predicted and experimental data. The applied methodology provides a differential equation that allows the inclusion of pH as a state variable of the system that can be easily included in a general mathematical model of anaerobic digestion using matrix notation. This methodology also allows a noticeable decrease in computing time in simulations. A dynamic anaerobic digestion model of complex substrates taken from the literature was completed with the developed algorithms, and it was used to predict the response of an anaerobic reactor against overloading and against the presence of pH-dependent inhibitors with satisfactory results.

Parameter identification of thermophilic anaerobic degradation of valerate.

The considered mathematical model of the decomposition of valerate presents three unknown kinetic parameters, two unknown stoichiometric coefficients, and three unknown initial concentrations for biomass. Applying a structural identifiability study, we concluded that it is necessary to perform simultaneous batch experiments with different initial conditions for estimating these parameters. Four simultaneous batch experiments were conducted at 55 degrees C, characterized by four different initial acetate concentrations. Product inhibition of valerate degradation by acetate was considered. Practical identification was done optimizing the sum of the multiple determination coefficients for all measured state variables and for all experiments simultaneously. The estimated values of kinetic parameters and stoichiometric coefficients were characterized by the parameter correlation matrix, the confidence interval, and the student's t-test at 5% significance level with positive results except for the saturation constant, for which more experiments for improving its identifiability should be conducted. In this article, we discuss kinetic parameter estimation methods.

Air stripping of ammonia from pig slurry: characterisation and feasibility as a pre- or post-treatment to mesophilic anaerobic digestion.

The objective of the present paper has been to study the effect of pig slurry waste type, fresh or anaerobically digested, and the effect of initial pH on ammonia air stripping from pig slurry waste at high temperature (80 degrees C). Stripping process as pre- or post-treatment to anaerobic digestion has been also evaluated. Treatment performances differ according to pig slurry type. When fresh pig slurry is used, despite working at 80 degrees C, a high initial pH (11.5) is required for complete ammonia removal. On the other hand, for digested pig slurry, complete ammonia removal without pH modification is possible and organic matter significantly less contaminates recovered ammonia salt. Batch anaerobic tests showed that ammonia air stripping is not an advisable pre-treatment to pig slurry anaerobic digestion.

Pig slurry concentration by vacuum evaporation: influence of previous mesophilic anaerobic digestion process.

Water can be removed from pig slurry by evaporation, through the application of wasted heat from a power plant or from other processes. Apart from obtaining a concentrate with an obviously higher nutrient concentration than the original slurry, another objective of water removal is to obtain water as condensate, which could be reused. The objective of this work was to study the vacuum evaporation of pig slurry liquid fraction and to evaluate condensate composition as a function of both pH (4, 5, and 6) and pig slurry type (fresh slurry and anaerobically digested slurry). Batch experiments showed that condensate characteristics, total ammonia nitrogen (NH3-N), volatile fatty acids (VFA), and chemical oxygen demand were strongly dependent on initial slurry pH. In addition to producing part of the required thermal energy, previous anaerobic digestion presented several other clear advantages. The consumption of VFA and other volatile organic compounds during anaerobic digestion reduced the volatilization of organic matter in the evaporation treatment and, consequently, provided a higher quality condensate.