Determination of the lipid content of organic waste using time-domain nuclear magnetic resonance.

Time-Domain Nuclear Magnetic Resonance (TD-NMR) was used to quantify the lipid contents of 48 different organic waste substrates. Results obtained from TD-NMR were compared to those from Soxhlet extraction, currently the prevalent method for organic waste characterization, especially in the field of anaerobic digestion. Two calibration methods were tested. The first was a self-calibration process using pure oils (NMR1) which showed good repeatability compared to Soxhlet extraction with a better coefficient of variation (5%). Analyses of volatile fatty acids (VFA) and long-chain fatty acids (LCFA) by chromatography were carried out to understand why the NMR1 method produced underestimations for some samples. Statistical analysis showed that the presence of saturated fatty acids had a significant effect on differences between the Soxhlet and NMR1 methods. The second calibration method applied chemometrics to TD-NMR raw data (NMR2), taking Soxhlet extraction values as references. It provided a good prediction of lipid content and avoided the lengthy calibration procedure usually required for this type of study. Last, the NMR2 method was shown to be highly suited to the quantification of lipids in organic waste, demonstrating better repeatability than the classic Soxhlet method.

A simple mass balance tool to predict carbon and nitrogen fluxes in anaerobic digestion systems.

The increase in anaerobic digestion systems has profoundly affected the waste management of territories, particularly for agricultural systems. Changes in cultural practices and imports of organic waste modify the carbon (C) and nitrogen (N) fluxes on territories where anaerobic digestion is implemented. Successful anaerobic digestion can increase the economic and ecological efficiency of the waste management system. Conversely, poor anaerobic digestion leads to low economic and environmental efficiency due to greenhouse gas emissions and nutrient loss. Modeling the impact of anaerobic digestion on the systems integrating anaerobic digestion can improve the efficiency of these practices. The aim of this study was to develop, analyze, and evaluate a simple mass balance tool able to predict carbon and nitrogen fluxes in anaerobic digestion systems. The tool is composed of an exhaustive substrate database used by three models: (i) an anaerobic digestion model that predicts C and N contents in biogas and digestate; (ii) a phase separation model that predicts C and N content in liquid and solid phase digestates; and (iii) a storage model that predicts C and N content in raw, liquid phase, and solid phase digestates, as well as C and N emissions during storage. Sensitivity analyses were performed on the tool to determine critical inputs. Sensitivity analysis showed that outputs were highly sensitive to their respective inputs and to total inputs of solids. Performance evaluation showed that the tool can provide good quality predictions with R2 correlations between observation and prediction varying from 0.72 to 0.99 with the best predictions obtained for raw digestate.

Modeling the fate of organic nitrogen during anaerobic digestion: Development of a bioaccessibility based ADM1.

Simulating the fate of nitrogen during anaerobic digestion is required to predict the characteristics of digestates and to improve their exploitation for agricultural uses. The aim of this study was to develop a modified ADM1 model that includes bioaccessibility-based fractionation to accurately simulate the fate of nitrogen during anaerobic digestion. To this end, two complementary approaches were used: (i) changes in the bioaccessibility of protein and non-protein compounds were assessed on eight substrates during anaerobic digestion in batch experiments using the "EPS" fractionation method; (ii) experimental results were used to develop a bio-kinetic model based on anaerobic digestion model n°1. This new model incorporates bioaccessibility-based fractionation in its input state variables. The model was successfully calibrated and model evaluation showed that predicted methane production, ammonium production and changes in protein and non-protein bioaccessibility during anaerobic digestion were accurate.

Characterization and prediction of organic nitrogen biodegradability during anaerobic digestion: A bioaccessibility approach.

Prediction of organic nitrogen mineralization into ammonium during anaerobic digestion is required for optimizing substitution of mineral fertilizer by digestates. The aim of this study was to understand organic nitrogen biodegradability and to investigate how it can be predicted from carbon biodegradability, and nitrogen bioaccessibility, respectively. Bioaccessibility was assessed using fractionation methods based on sequential extractions. Results showed that organic nitrogen was present in fractions whose bioaccessibility levels differed. Organic nitrogen and carbon biodegradability were also determined and compared. Results highlighted two groups of substrates: the first with an initial NH4+/TKN < 30%, whose carbon and nitrogen biodegradability are similar; the second with an initial NH4+/TKN > 30%, whose carbon and nitrogen biodegradability differ significantly. To enable prediction on all substrates, partial least square (PLS) regressions were carried out to link organic nitrogen bioaccessibility indicators to biodegradability. The models successfully predicted organic nitrogen biodegradability with a maximum prediction error of 10%.

Comparison of existing models to simulate anaerobic digestion of lipid-rich waste.

Models for anaerobic digestion of lipid-rich waste taking inhibition into account were reviewed and, if necessary, adjusted to the ADM1 model framework in order to compare them. Experimental data from anaerobic digestion of slaughterhouse waste at an organic loading rate (OLR) ranging from 0.3 to 1.9kgVSm-3d-1 were used to compare and evaluate models. Experimental data obtained at low OLRs were accurately modeled whatever the model thereby validating the stoichiometric parameters used and influent fractionation. However, at higher OLRs, although inhibition parameters were optimized to reduce differences between experimental and simulated data, no model was able to accurately simulate accumulation of substrates and intermediates, mainly due to the wrong simulation of pH. A simulation using pH based on experimental data showed that acetogenesis and methanogenesis were the most sensitive steps to LCFA inhibition and enabled identification of the inhibition parameters of both steps.

Modelling the rheological properties of sludge during anaerobic digestion in a batch reactor by using electrical measurements.

Anaerobic digestion is a significant process leading to biogas production and waste management. Despite this double interest, professionals still face a lack of efficient tools to monitor and manage the whole procedure. This is especially true for rheological properties of the material inside the reactor, which are of major importance for anaerobic digestion management. However, rheological properties can hardly be determined in-situ and it would be very helpful to determine indicators of their evolution. To solve this problem, this paper investigates the evolution of sewage sludge rheological and electrical properties during the anaerobic digestion in a batch reactor. We especially focus on apparent viscosity and complex impedance, measured by electrical impedance spectroscopy. Both of them can be modelled by a linear combination of raw sludge and inoculum properties, weighted by time-dependent coefficients. Thus, by determining digested sludge electrical signature, it is possible to obtain those coefficients and model sludge apparent viscosity. This work offers many theoretical and practical prospects.

A waste characterisation procedure for ADM1 implementation based on degradation kinetics.

In this study, a procedure accounting for degradation kinetics was developed to split the total COD of a substrate into each input state variable required for Anaerobic Digestion Model n°1. The procedure is based on the combination of batch experimental degradation tests ("anaerobic respirometry") and numerical interpretation of the results obtained (optimisation of the ADM1 input state variable set). The effects of the main operating parameters, such as the substrate to inoculum ratio in batch experiments and the origin of the inoculum, were investigated. Combined with biochemical fractionation of the total COD of substrates, this method enabled determination of an ADM1-consistent input state variable set for each substrate with affordable identifiability. The substrate to inoculum ratio in the batch experiments and the origin of the inoculum influenced input state variables. However, based on results modelled for a CSTR fed with the substrate concerned, these effects were not significant. Indeed, if the optimal ranges of these operational parameters are respected, uncertainty in COD fractionation is mainly limited to temporal variability of the properties of the substrates. As the method is based on kinetics and is easy to implement for a wide range of substrates, it is a very promising way to numerically predict the effect of design parameters on the efficiency of an anaerobic CSTR. This method thus promotes the use of modelling for the design and optimisation of anaerobic processes.

Anaerobic co-digestion of waste activated sludge and greasy sludge from flotation process: batch versus CSTR experiments to investigate optimal design.

In this study, the maximum ratio of greasy sludge to incorporate with waste activated sludge was investigated in batch and CSTR experiments. In batch experiments, inhibition occurred with a greasy sludge ratio of more than 20-30% of the feed COD. In CSTR experiments, the optimal greasy sludge ratio was 60% of the feed COD and inhibition occurred above a ratio of 80%. Hence, batch experiments can predict the CSTR yield when the degradation phenomenon are additive but cannot be used to determine the maximum ratio to be used in a CSTR configuration. Additionally, when the ratio of greasy sludge increased from 0% to 60% of the feed COD, CSTR methane production increased by more than 60%. When the greasy sludge ratio increased from 60% to 90% of the feed COD, the reactor yield decreased by 75%.

Combination of batch experiments with continuous reactor data for ADM1 calibration: application to anaerobic digestion of pig slurry.

Modelling anaerobic digestion processes is a key aspect of studying and optimizing digesters and related waste streams. However, for the satisfactory prediction of biogas production and effluent characteristics, some parameters have to be calibrated according to the characteristics of the substrates. This article describes a calibration procedure for the IWA 'Anaerobic Digestion Model no. 1' applied to the modelling of a digester for treatment of pig slurry. The most sensitive parameters were selected and calibrated combining results from a continuous digester and from batch trials run with the sludge sampled from the digester and the addition of specific substrates. According to the sensitivity analysis, acetoclastic methanogenesis, acetogenesis of propionate and acidogenesis of sugars were identified as the main sensitive steps in our case. The calibration procedure led us to modify slightly acetogenesis of propionate kinetic. However, acetoclastic methanogenesis and acidogenesis of sugars kinetics were significantly reduced by decreasing km and increasing Ks. Indeed, for instance, a decrease of km_ac from 8 to 7 day(-1) combined with an increase of Ks_ac from 0.15 to 1.5 kgCOD/m3 was necessary. After calibration, ADM1 provides an accurate simulation of the continuous reactor results.

Sulphur fate and anaerobic biodegradation potential during co-digestion of seaweed biomass (Ulva sp.) with pig slurry.

Seaweed (Ulva sp.) stranded on beaches were utilized as co-substrate for anaerobic digestion of pig slurry in three-month co-digestion tests in pilot scale anaerobic digesters in the laboratory. The methanogenic potential of Ulva sp. was low compared to that of other potential co-substrates available for use by farmers: 148 N m3CH4/t of volatile solids or 19 N m3CH4/t of crude product. When used as a co-substrate with pig manure (48%/52% w/w), Ulva sp. seaweed did not notably disrupt the process of digestion; however, after pilot stabilisation, biogas produced contained 3.5% H2S, making it unsuitable for energy recovery without treatment. Sequentially addition of the sulphate reduction inhibitor, potassium molybdate, to a final concentration of 3mM, temporarily reduced H2S emissions, but was unable to sustain this reduction over the three-month period. According to these pilot tests, the use of seaweed stranded on beaches as co-substrate in farm-based biogas plants shows some limitations.

Identification and partial characterization of proteins and proteoglycans encrusting the secondary cell walls of flax fibres.

Four proteins were isolated from depectinised elementary fibres of flax (Linum usitatissimum L.), using either alkali or cellulase digestion treatments. All the four proteins were characterized by a deficiency or low contents of hydroxyproline and by high levels of glutamic acid/glutamine and/or aspartic acid/asparagine. The two proteoglycans solubilized with cellulase strongly reacted with beta-glucosyl Yariv reagent but not with alpha-glucosyl Yariv reagent and contained appreciable amounts of alanine, glycine, serine and threonine, suggesting a relationship with cell wall hydroxyproline-deficient arabinogalactan-proteins. The two alkali-extracted proteins did not show any reaction with beta-glucosyl Yariv dye. Due to the harsh treatment, they might only partially represent the original proteins. Due to its high level of glycine (41%), one of these proteins might be classified as a glycine-rich protein. The latter polypeptide, of low molecular molar mass, contained 14.6% leucine and might consist of a domain related to leucine-rich proteins. The data show that these proteins and arabinogalactan-protein-like proteoglycans were strongly associated with the secondary walls of flax fibres. Their presence in small amounts (0.1-0.4%), raises the problem of their putative structural role.

Galactans and cellulose in flax fibres: putative contributions to the tensile strength.

The proton spin-spin relaxation time, T2, measured from solid-state NMR, indicates a greater rigidity for cellulose than for the adhesive matrix between the microfibrils of flax ultimate fibres. Cytochemical and biochemical analyses allow the identification of: (1) EDTA-soluble RG I-polymers in the primary walls and cell junctions of fibres; (2) long 1 --> 4-beta-D-galactan chains between primary and secondary wall layers; and (3) arabinogalactan-proteins throughout the secondary walls. These polymers in the adhesive matrix between microfibrils and/or cellulose layers ensure that cracks propagate along the matrix rather than across the fibres and play an important role in allowing flax fibres to approach the tensile strength of advanced synthetic fibres like carbon and Kevlar.