The fate of Cu and Zn along the feed-animal-excreta-effluent continuum in swine systems according to feed and effluent treatment strategies.

Copper (Cu) and zinc (Zn) have negative environmental impacts as they accumulate in the soil after pig manure is spread. Cu and Zn are essential elements in pig nutrition but due to their low retention rate, more than 90% of ingested Cu and Zn are excreted. A better understanding of the behaviour of these elements throughout the animal-manure-soil continuum according to feed composition and manure management chain is thus required to propose alternative ways to reduce these environmental impacts. The aim of this study was to determine the fate of Cu and Zn throughout this continuum by studying the effect of Cu and Zn contents in animal feed and in the manure management chain based on anaerobic digestion and composting. Faeces were collected from 24 finishing pigs fed with 4 different Cu and Zn dietary levels and sources of supplementation. Samples of faeces were exposed to mesophilic anaerobic digestion or to 5-week composting with straw. Concentrations of Cu and Zn in the faeces were highly dependent on dietary supplies and ranged from 38 to 188 mg Cu/kg DM and from 191 to 728 mg Zn/kg DM. Degradation of a significant fraction of organic matter during treatment led to a significant increase in Cu and Zn concentration relative to the product's dry matter (DM) content, which. Cu and Zn concentrations relative to DM content were twice as high after treatment whatever the content and the form of Cu and Zn dietary supplementation. Otherwise, effluent treatment tended to reduce the possible availability of Cu and Zn in final organic products according to water-extractible contents. This study clearly shows that feed management is the main lever for reducing the amount of Cu and Zn amount in pig effluents and hence in the soil. Appropriate treatment could also facilitate the supply of organic fertilisers to areas with soil deficiency, but feed strategies need to be adapted to the treatment chain to enable the production of good quality organic products that respect EU regulations.

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.

Fault detection with moving window PCA using NIRS spectra for monitoring the anaerobic digestion process.

Principal component analysis (PCA) is a popular method for process monitoring. However, most processes are time-varying, thus older samples are not representative of the current process status. This led to the introduction of adaptive-PCA based monitoring, such as moving window PCA (MWPCA). In this study, near-infrared spectroscopy (NIRS) responses to digester failures were evaluated to develop a spectral data processing tool. Tests were performed with a spectroscopic probe (350-2,500 nm), using a 35 L mesophilic continuously stirred tank reactor. Co-digestion experiments were performed with pig slurry mixed with several co-substrates. Different stresses were induced by abruptly increasing the organic load rate, changing the feedstock or stopping the stirring. Physicochemical parameters as well as NIRS spectra were acquired for lipid, organic and protein overloads experiments. MWPCA was then applied to the collected spectra for a multivariate statistical process control. MWPCA outputs, Hotelling T2 and residuals Q statistics showed that most of the induced dysfunctions can be detected with variations in these statistics according to a defined criterion based on spectroscopic principles and the process. MWPCA appears to be a multivariate statistical method that could help in decision support in industrial biogas plants.

Detection of early imbalances in semi-continuous anaerobic co-digestion process based on instantaneous biogas production rate.

The aim of this study was to investigate the use of biogas production rate kinetics for the monitoring of anaerobic co-digestion. Recent extensive studies of degradation pathways showed that acetoclastic methanogenesis is not always the main pathway. Hydrogenotrophic methanogenesis and syntrophic acetate oxidation can also dominate, mostly for operating conditions with high concentrations of ammonia or volatile fatty acids … These conditions are also known to cause instability in the digester's operation especially in co-digestion due to substrate variability. Therefore, co-digestion experiments were conducted with several co-substrates using a continuously stirred 35-L tank reactor. Degradation pathways and their potential shifts were identified by monitoring variations in biogas production rate kinetics using a principal component analysis model. The shifts in the degradation pathways were used to monitor the process. These shift points were found to provide early warnings of instabilities in the anaerobic co-digestion process.

Long chain fatty acids (LCFA) evolution for inhibition forecasting during anaerobic treatment of lipid-rich wastes: Case of milk-fed veal slaughterhouse waste.

A detailed study of a solid slaughterhouse waste (SHW) anaerobic treatment is presented. The waste used in this study is rich in lipids and proteins residue. Long chain fatty acids (LCFA), coming from the hydrolysis of lipids were inhibitory to anaerobic processes at different degrees. Acetogenesis and methanogenesis processes were mainly affected by inhibition whereas disintegration and hydrolysis processes did not seem to be affected by high LCFA concentrations. Nevertheless, because of the high energy content, this kind of waste is very suitable for anaerobic digestion but strict control of operating conditions is required to prevent inhibition. For that, two inhibition indicators were identified in this study. Those two indicators, LCFA dynamics and LCFA/VSbiomass ratio proved to be useful to predict and to estimate the process inhibition degree.

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.

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.

Modelling of manure production by pigs and NH3, N2O and CH4 emissions. Part II: effect of animal housing, manure storage and treatment practices.

A model has been developed to predict pig manure evolution (mass, dry and organic matter, N, P, K, Cu and Zn contents) and related gaseous emissions (methane (CH4), nitrous oxide (N2O) and ammonia (NH3)) from pig excreta up to manure stored before spreading. This model forms part of a more comprehensive model including the prediction of pig excretion. The model simulates contrasted management systems, including different options for housing (slatted floor or deep litter), outside storage of manure and treatment (anaerobic digestion, biological N removal processes, slurry composting (SC) with straw and solid manure composting). Farmer practices and climatic conditions, which have significant effects on gaseous emissions within each option, have also been identified. The quantification of their effects was based on expert judgement from literature and local experiments, relations from mechanistic models or simple emission factors, depending on existing knowledge. The model helps to identify relative advantages and weaknesses for each system. For example, deep-litter with standard management practices is associated with high-greenhouse gas (GHG) production (+125% compared to slatted floor) and SC on straw is associated with high NH3 emission (+15% compared to slatted floor). Another important result from model building and first simulations is that farmer practices and the climate induce an intra-system (for a given infrastructure) variability of NH3 and GHG emissions nearly as high as inter-system variability. For example, in deep-litter housing systems, NH3 and N2O emissions from animal housing may vary between 6% and 53%, and between 1% and 19% of total N excreted, respectively. Thus, the model could be useful to identify and quantify improvement margins on farms, more precisely or more easily than current methodologies.

Combined anaerobic digestion and biological nitrogen removal for piggery wastewater treatment: a modelling approach.

In order to deal with the environmental problems associated with animal production industrialization and at the same time considering energy costs increasing, a piggery wastewater treatment process consisting of combined anaerobic digestion and biological nitrogen removal by activated sludge was developed. This contribution presents a modelling framework in order to optimize this process. Modified versions of the well established ASM1 and ADM1 models have been used. The ADM1 was extended with biological denitrification. pH calculation and liquid gas-transfer were modified to take into account the effect of associated components. Finally, two interfaces (ADMtoASM and ASMtoADM) were built in order to combine both models. These interfaces set up the COD, nitrogen, alkalinity and charge fractionation between both models. However, for the mass balances between both models, some hypotheses were considered and might be evaluated.

The efficiency of biological aerobic treatment of piggery wastewater to control nitrogen, phosphorus, pathogen and gas emissions.

Due to the water pollution and in order to reduce the nitrogen load applied on soils, biological nitrogen removal treatment of piggery wastewaters was developed in Brittany (France), with 250-300 units running. Four types of treatment processes were built including a biological reactor allowing to remove about 60-70% of the nitrogen content as gas by nitrification/denitrification. The addition of different mechanical separators (screw-press, centrifuge decanter ...) led to concentration of phosphorus in an exportable solid phase, allowing a reduction up to 80% of the phosphorus applied locally on soils. Moreover, a reduction of the gaseous emissions was observed using this management process as compared to conventional management (storage + land spreading) including ammonia (up to 68%) and greenhouse gases (55%). Finally, the level of enteric and pathogenic bacteria was also decreased with the treatment process as compared to conventional management systems. However, in spite of these results, the significant cost of the treatment must be underlined and alternative systems including anaerobic digestion will have to be studied.

The effect of incubation conditions on the laboratory measurement of the methane producing capacity of livestock wastes.

The effects of incubations conditions (dilution, mixing, incubation time and inoculum amount and origin) on the determination of the maximum methane producing capacity (B(0)) from various livestock slurries were evaluated. For this purpose, the methane yields of different livestock slurries were determined using batch anaerobic incubations performed at 30 degrees C as regard these different conditions. The B(0) and the methane (CH(4)) generation as a function of time were used to study the processes and to determine the best incubation conditions. Methanogenesis was identified as the major rate-limiting step during the anaerobic degradation of slurries, probably due to inhibition by volatile fatty acids. In some cases, high free NH(3) concentrations were suspected to inhibit the hydrolysis process. The addition of inoculum and/or the dilution of the substrate reduced the inhibition and allowed to reach the B(0) more rapidly. However, the addition of inoculum must be minimized to reduce the possible errors made by considering a similar production by the inoculum with and without the substrate. All experiments performed during this study allowed to define the incubation conditions required for the determination of the B(0) from livestock slurries. Applying these conditions, the B(0) values determined for swine slurries varied from 244 to 343L CH(4)kg V(added)(-1), from 204 to 296L CH(4)kg V(added)(-1) for dairy cattle slurries and equalled 386 and 319L CH(4)kg VS(added)(-1) respectively for calves and duck slurries.

Modelling of biological nitrogen removal during treatment of piggery wastewater.

During this study, a mathematical model simulating piggery wastewater treatment was developed, with the objective of process optimisation. To achieve this, the effect of temperature and free ammonia concentration on the nitrification rate were experimentally studied using respirometry. The maximum growth rates obtained were higher for ammonium-oxidising biomass than for nitrite-oxidising biomass for the temperatures above 20 degrees C; values at 35 degrees C were equal to 1.9 and 1.35 day(-1), respectively. No inhibition of nitrification was observed for free ammonia concentrations up to 50 mgN/L. Using these data with others experimental data obtained from a pilot-scale reactor to treat piggery wastewater, a model based on a modified version of the ASM1 was developed and calibrated. In order to model the nitrite accumulation observed, the ASM1 model was extended with a two-step nitrification and denitrification including nitrite as intermediate. Finally, the produced model called PiWaT1 demonstrated a good fit with the experimental data. In addition to the temperature, oxygen concentration was identified as an important factor influencing the nitrite accumulation during nitrification. Even if some improvements of the model are still necessary, this model can already be used for process improvement.

Modelling of biological processes during aerobic treatment of piggery wastewater aiming at process optimisation.

A dynamic mathematical model was developed for the simulation of the aerobic treatment of piggery wastewater. This model includes the carbon oxidation, the nitrification and the denitrification. According to the experimental results obtained during this study, a modified version of the activated sludge model No. 1 has been developed. The model includes (1) nitrite as intermediate of nitrification and denitrification, (2) the distinction between the anoxic heterotrophic yield and the aerobic heterotrophic yield, respectively equal to 0.53 and 0.6 and (3) the first-order hydrolysis of the slowly biodegradable fraction. The calibration and the validation of the model was performed using experimental data from three experiments with two piggery wastewaters. A set of kinetic and stoichiometric parameters emerged from these tests. Except the kinetic of hydrolysis of the slowly biodegradable organic matter varying from 6 to 25 gCOD(gCODday)(-1), all other parameters were similar for all experiments. The dissolved oxygen concentration was identified as the main variable influencing the nitrite accumulation during nitrification. In the calibrated model, the oxygen half-saturation coefficient of the ammonium oxidisers (0.3g O(2)m(-3)) was lower than for the nitrite oxidisers (1.1 gO(2)m(-3)), leading to nitrite accumulation when the dissolved oxygen concentration was low. Simulations with the proposed model could be very useful for improved design and management of biological treatment of piggery wastewaters, particularly in case of partial nitrification to nitrite directly followed by denitrification.

In situ measurement of ammonia and greenhouse gas emissions from broiler houses in France.

An experimental technique was developed for measuring gaseous emissions including ammonia (NH(3)), nitrous oxide (N(2)O) and methane (CH(4)) from broiler houses. This technique included the monitoring of the air flow rate and the gaseous concentrations. NH(3) was determined using acid trap while N(2)O and CH(4) were determined continuously by infrared gas analyser and sequentially by gas chromatography. Moreover, N(2)O and CH(4) emissions were monitored above the litter using closed flux chambers at the end of the experiment. No emissions of N(2)O and CH(4) were observed neither during the growth of the broiler nor above the litter at the end of the experiment. Ammonia concentration varied between 0.8 and 32 ppm in the building. Total ammonia emissions were estimated to 5.74 g N animal(-1) during this experiment. According to this result, ammonia emissions from broiler houses could be estimated to 5.3 kt of N per year in France.

Piggery wastewater characterisation for biological nitrogen removal process design.

In intensive farming areas, the design of biological nitrogen removal plants for piggery wastewater requires the determination of the chemical oxygen demand (COD) fractions of the effluent. For this purpose, an experimental procedure was developed to quantify the inert soluble (SI) and particulate (XI) COD fractions, as well as the readily (SS) and the slowly (XS) biodegradable COD fractions. For the four wastewaters tested, the SI and the XI fractions were equal to 3-4 g O(2)l(-1) and 17-28 g O(2)l(-1), respectively, which resulted in a total inert fraction of 42-84% of total COD. The SS and the XS fractions were very variable, ranging 0-5 g O(2)l(-1) and 4-25 g O(2)l(-1) respectively, depending on the farm management practices and the storage conditions prior to biological treatment. From these results, the denitrification potential of the piggery wastewaters for biological nitrogen removal treatment could be assessed.

Activated Sludge Model No. 1 calibration for piggery wastewater treatment using respirometry.

To optimise the intermittent aeration process for piggery wastewater, the Activated Sludge Model No. 1 needs to be calibrated and adapted to this specific effluent. By combining aerobic and anoxic respirometric tests, biodegradation kinetics of organic fractions in piggery wastewater could be studied. Modeling of the respirometric curves proved that the simplified hydrolysis model was sufficient for piggery wastewater treatment simulation. The hydrolysis constant (K(H)) and heterotrophic sludge yield (Y(H)) were determined at temperature and pH in the ranges 10-40 degrees C and 7-9, respectively. The constants were slightly influenced by the temperature but not significantly affected by the pH, with average values of 3 d(-1) for K(H) and 0.60 for Y(H). The anoxic respirometric tests revealed that the experimental ASM1 anoxic correction factor (eta(g)) was higher than one. This could be explained by the fact that the anoxic and the aerobic heterotrophic sludge yields were probably different. By fixing a value of 0.8 for eta(g), the anoxic sludge yield (Y(HD)) could be calculated at 0.53. A modified version of ASM1 for substrate biodegradation in piggery wastewater intermittent aeration process was proposed, including the separation between the anoxic and the aerobic sludge yields and a simplified hydrolysis kinetic.

Fate of phosphorus from biological aerobic treatment of pig slurry. By-products characterization and recovery.

The fate of phosphorus distribution in the products obtained from biological aerobic treatment of pig slurry, e.g. separated solids, liquid effluent and sludge, was monitored in three different farm-scale units. Samples of raw slurry, solid products, aerated slurry, liquid effluent and sludge were characterised and analysed for their concentration in total phosphorus, nitrogen content and heavy metals (Cu and Zn). At each treatment stage, nitrogen, phosphorus and heavy metals mass balance between input and output was established. Moreover, liquid products were characterised and analysed both for their total and dissolved ortho-phosphate content. Separated solids, sludge and liquid effluent represented 5%, 15-40% and 75-83% of the mass of the raw slurry, respectively. A mechanical separation step prior to aeration allowed the export of 25-30% of total phosphorus for further use as organic fertiliser. A large amount of total phosphorus (e.g. 60-70%) was located in sludge while phosphorus remaining in liquid effluent was about 15-25%. Raw slurry separation and sufficient aeration allowed phosphorus to concentrate in the sludge. Insufficient aeration resulted in the release of phosphorus as dissolved ortho-phosphate within the liquid effluent. Finally, relevance of the agronomic use of the products was discussed and improvements of biological aerobic treatment to enhance phosphorus removal and/or recovery were considered.