Chemical and odor characterization of gas emissions released during composting of solid wastes and digestates.

Hazardous and odorous gas emissions from composting and methanization plants are an issue of public concern. Odor and chemical monitoring are thus critical steps in providing suitable strategies for air pollution control at waste treatment units. In this study, 141 gas samples were extensively analyzed to characterize the odor and chemical emissions released upon the aerobic treatment of 10 raw substrates and five digestates. For this purpose, agricultural wastes, biowastes, green wastes, sewage sludge, and municipal solid waste (MSW) were composted in 300 L pilots under forced aeration. Gas exhausts were evaluated through dynamic olfactometry and analytical methods (i.e., GC/MS) to determine their odor concentration (OC in OUE m-3) and chemical composition. A total of 60 chemical compounds belonging to 9 chemical families were identified and quantified. Terpenes, oxygenated compounds, and ammonia exhibited the largest cumulative mass emission. Odor emission rates (OUE h-1) were computed based on OC measurements and related to the initial amount of organic matter composted and the process time to provide odor emission factors (OEFs in OUE g-1OM0). The composting process of solid wastes accounted for OEFs ranging from 65 to 3089 OUE g-1OM0, whereas digestates composting showed a lower odor emission potential with OEF fluctuating from 8.6 to 30.5 OUE g-1OM0. Moreover, chemical concentrations of single compounds were weighted with their corresponding odor detection thresholds (ODTs) to yield odor activities values (OAVs) and odor contribution (POi, %). Volatile sulfur compounds were the main odorants (POi = 54-99%) regardless of the operational composting conditions or substrate treated. Notably, methanethiol was the leading odorant for 73% of the composting experiments.

Toluene biodegradation in a solid/liquid system involving immobilized activated sludge and silicone oil as pollutant reservoir.

A solid/liquid system involving activated sludge immobilized in an agar medium and a non-aqueous phase liquid containing the target pollutant has been considered to treat a model hydrophobic volatile organic compound, toluene. The positive impact of the use of a multiphase bioreactor is that the organic phase constitutes a pollutant reservoir and also helps to overcome possible pollutant toxicity. In addition and to overcome the drawbacks of the use of a solid organic phase (high pressure drop and low mass transfer) instead of a liquid organic phase, the considered solid phase was the aqueous. Consequently, silicone oil (polydimethylsiloxane) which showed its relevance for implementation in multiphase bioreactors was used. Promising results were observed from the analysis of toluene in the gaseous phase; for an initial amount of 2 g L(-1) related to the organic phase, a v/v ratio of 0.5 of the organic phase to the aqueous agar phase, total toluene consumption was observed in about 9 days, leading to a global biodegradation rate of approximately 3.1 mg L(-1) h(-1), namely in the range of values previously observed in liquid/liquid systems.

Biodegradation of toluene in a two-phase partitioning bioreactor--impact of activated sludge acclimation.

A two-phase partitioning bioreactor was considered to remove toluene contained in a biodegradable organic phase by activated sludge (AS). The selected solvent was hexadecane. In a first step, the biodegradation of toluene dissolved in hexadecane by AS was examined. In a second step, acclimation of the AS was carried out in order to improve the biodegradation rate. Acclimation improved toluene removal, since biodegradation yield increased from 72% to more than 91%. A total consumption was observed after only 4 days culture with acclimated AS, since the rest of the toluene corresponded to gas leak; while in the case of non-acclimated sludge, losses cannot account for all non-degraded toluene. Regarding hexadecane, acclimation also improved its degradation, from 43% to 79% after 6 days culture for non-acclimated and acclimated AS, respectively.

Relevance of an organic solvent for absorption of siloxanes.

A wide range of siloxanes exist but the most abundant in biogas are Hexamethyldisiloxane (L2) and Octamethyltrisiloxane (L3) as linear siloxanes and Octamethylcyclotetrasiloxane (D4) as a cyclic siloxane. In order to remove volatile organic compound from biogas, different processes can be used. A promising process for siloxane removal is their absorption in an organic solvent. In this work, three oils were tested to absorb the selected siloxanes: silicone oil 47V20, Seriola 1510 and Polyalphaolefin. Initially, the characterization of these oils was realized by measuring their viscosities and densities, depending on temperature. The second time, the absorption capacity of the siloxanes by selected oils was characterized through the determination of their Henry's constants, but also owing to the implementation of a wet-wall column. Both Henry's constants and removal efficiencies in continuous regime revealed that silicone oil (47V20) can be considered as the most efficient oil among the three selected siloxanes. Moreover, the cyclic siloxane (D4) showed more affinity with oils than linear siloxanes. Silicone oil 47V20 appeared to be the best oil (intermediate price 14 euro/L, low viscosity, low volatility, chemical inertness (no corrosion) and resistance to high and low temperatures).

Simulation of hydrogen sulphide absorption in alkaline solution using a packed column.

In this work, a simulation tool was developed for hydrogen sulphide (H2S) removal in an alkaline solution in packed columns working at countercurrent. Modelling takes into account the mass-transfer enhancement due to the reversible reactions between H2S and the alkaline species (CO(²â»)(3), HCO⁻(3), and HO⁻) in the liquid film. Many parameters can be controlled by the user such as the gas and liquid inlet H2S concentrations, the gas and liquid flow rates, the scrubbing liquid pH, the desired H2S removal efficiency, the temperature, the alkalinity, etc. Since the influence of the hydrodynamic and mass-transfer performances in a packed column is well known, the numerical resolutions performed were dedicated to the study of the influence of the chemical conditions (through the pH and the alkalinity), the temperature and the liquid-to-gas mass flow rate ratio (L/G). A packed column of 3 m equipped with a given random packing material working at countercurrent and steady state has been modelled. The results show that the H2S removal efficiency increases with the L/G, the pH, the alkalinity and more surprisingly with the temperature. Alkalinity has a very significant effect on the removal efficiency through the mass-transfer enhancement and buffering effect, which limits pH decreasing due to H2S absorption. This numerical resolution provides a tool for designers and researchers involved in H2S treatment to understand deeper the process and optimize their processes.

New insights into biochar ammoniacal nitrogen adsorption and its correlation to aerobic degradation ammonia emissions.

One of the technical barriers to the wider use of biochar in the composting practices is the lack of accurate quantification linking biochar properties to application outcomes. To address this issue, this paper investigates the use of ammonia nitrogen adsorption capacity by biochar as a predictor of ammonia emission during composting in the presence of biochar. With this in mind, this work investigated the use of ammonia nitrogen adsorption capacity of biochar when mixed with solid digestate, and the reduction in ammonia emissions resulting from the addition of biochar during aerobic degradation of solid digestate. A biochar synthesized at 900 °C, another synthesized at 450 °C, and two derivatives of the latter biochar, one chemically modified with nitric acid and the other with potassium hydroxide, were tested. This study concluded that the chemical characteristics of the biochar, including pH and oxygen/carbon atomic ratio, had a greater influence on the adsorption of ammonia nitrogen than physical attributes such as specific surface area. In this regard, nitric acid modification had superior performance compared to hydroxide potassium modification to increase biochar chemical attributes and reduce ammonia emissions when applied to aerobic degradation. Finally, a significant linear correlation (p-value < 0.05, r2 = 0.79) was found between biochar ammonia nitrogen adsorption capacity and ammonia emissions along composting, showing the potential of this variable as a predictive parameter. This study provides insights for future explorations aiming to develop predictive tests for biochar performance.

Enzymatic degradation of Congo Red by turnip (Brassica rapa) peroxidase.

The enzyme peroxidase is known for its capacity to remove phenolic compounds and aromatic amines from aqueous solutions and also to decolourize textile effluents. This study aims at evaluating the potential of a turnip (Brassica rapa) peroxidase (TP) preparation in the discolouration of textile azo dyes and effluents. An azo dye, Congo Red (CR), was used as a model pollutant for treatment by the enzyme. The effects of various operating conditions like pH value, temperature, initial dye and hydrogen peroxide concentrations, contact time, and enzyme concentration were evaluated. The optimal conditions for maximal colour removal were at pH 2.0, 40 degrees C, 50 mM hydrogen peroxide, 50 mg/l CR dye, and TP activity of 0.45 U/ml within 10 min of incubation time. Analysis of the by-products from the enzymatic treatment by UV-Vis and IR spectroscopy showed no residual compounds in the aqueous phase and a precipitate of polymeric nature.

Peroxidase enzymes as green catalysts for bioremediation and biotechnological applications: A review.

The fast-growing consumer demand drives industrial process intensification, which subsequently creates a significant amount of waste. These products are discharged into the environment and can affect the quality of air, degrade water streams, and alter soil characteristics. Waste materials may contain polluting agents that are especially harmful to human health and the ecosystem, such as the synthetic dyes, phenolic agents, polycyclic aromatic hydrocarbons, volatile organic compounds, polychlorinated biphenyls, pesticides and drug substances. Peroxidases are a class oxidoreductases capable of performing a wide variety of oxidation reactions, ranging from reactions driven by radical mechanisms, to oxygen insertion into CH bonds, and two-electron substrate oxidation. This versatility in the mode of action presents peroxidases as an interesting alternative in cleaning the environment. Herein, an effort has been made to describe mechanisms governing biochemical process of peroxidase enzymes while referring to H2O2/substrate stoichiometry and metabolite products. Plant peroxidases including horseradish peroxidase (HRP), soybean peroxidase (SBP), turnip and bitter gourd peroxidases have revealed notable biocatalytic potentialities in the degradation of toxic products. On the other hand, an introduction on the role played by ligninolytic enzymes such as manganese peroxidase (MnP) and lignin peroxidase (LiP) in the valorization of lignocellulosic materials is addressed. Moreover, sensitivity and selectivity of peroxidase-based biosensors found use in the quantitation of constituents and the development of diagnostic kits. The general merits of peroxidases and some key prospective applications have been outlined as concluding remarks.

Bio-based and cost effective method for phenolic compounds removal using cross-linked enzyme aggregates.

This work aimed at presenting a green method using a new source of peroxidase isolated from Raphanus sativus var. niger (RSVNP) in immobilized form, for the treatment of wastewater. To ensure stability and enzymatic activity in the biodegradation process, RSVNP was immobilized as a cross-linked enzyme aggregate (CLEAs). With more than 29% of recovered activity and 85% aggregation yield, acetone was selected as the best precipitating agent. The formed protein aggregates required 2% (v/v) of glutaraldehyde (GA) concentration and a ratio of 9:1 (v/v) enzyme (E) amount to cross-linker (E/GA). Compared to the free enzyme, RSVNP-CLEAs were found more chemically and thermally stable and exhibited good storage stability for more than 8 weeks. In addition, RSVNP-CLEAs were evaluated for their ability to remove phenol and p-cresol from aqueous solution by varying several operating conditions. A maximal yield (98%) of p-cresol conversion was recorded after 40 min; while 92% of phenol was degraded after 1 h duration time. The reusability of RSVNP-CLEAs was tested, displaying 71% degradation of phenol in the third batch carried out and more than 54% was achieved for p-cresol after four successive reuses in the presence of hydrogen peroxide at 2 mM concentration.

Co-current and counter-current spraying of odour-neutralizing products.

A lab-scale pilot plant was developed in order to measure the efficiency of some odour-neutralizing products for the removal of odorous compounds. Experiments were carried out on gas and liquid flows in two configurations: co-current and counter-current, which differ in the values of the drop diameter and the contact time, leading to different behaviours between highly water-soluble compounds like ammonia and other compounds like sulphurous compounds. Mass transfer was shown to be modified by the presence of neutralizing products as a result of their pH and surface tension. Few chemical reactions, except for acidic or basic ones, could be highlighted. Olfactometric analyses were carried out and showed that, because of possible confusion between odours caused by the neutralizing product and odours caused by the by-products, it was difficult to conclude that an obvious relation existed between physico-chemical and olfactometric efficiencies.

A combination of absorption and enzymatic biodegradation: phenol elimination from aqueous and organic phase.

Peroxidase from Brassica rapa was immobilized as cross-linked enzyme aggregates (CLEAs) and used to treat air containing phenol as a model molecule of volatile organic compounds (VOCs). Prior to an enzymatic treatment, phenol was absorbed into an aqueous or organic phase (silicone oil) to reach concentrations ranging from 20 to 160 mg/L. The process was carried out by introducing a desired weighing of BRP-CLEAs into preparations and reaction was started by injecting H2O2 solution to the medium. Optimization of the reaction conditions in the organic solvent revealed an optimal contact time of 60 min, 60 mg/L of phenol concentration and 3 mM H2O2, leading to a maximum removal yield of 70% for 3.4 UI/mL of BRP-CLEAs. These results were compared to those obtained in an aqueous medium that showed 90% of degradation yield after 40 min in the following conditions, 90 mg/L of initial phenol amount, 2 mM of H2O2 and 2.5 UI/mL of BRP-CLEAs. Parameters of the Michaelis-Menten model, Km and Vmax, were also determined for the reaction in both phases. Phenol removal by BRP-CLEAs in silicone oil succeeded with 70% of conversion yield. It is promising regarding the transposition of such enzymatic process to hydrophobic VOCs.

Odor generation patterns during different operational composting stages of anaerobically digested sewage sludge.

This study aimed to evaluate the global patterns of odor generation and odorant composition for different operational stages of anaerobically digested sewage sludge (ADS) composting at pilot scale. To this end, gas emissions were sampled and analyzed during storage, forced aeration treatment (active phase), turning process and curing. For each operational stage, odors were monitored by measuring the odor emission rates (OER in OUE h-1 kg-1ADS) through dynamic olfactometry and computing the odor activity values (OAVs) of compounds quantified by analytical methods (i.e., GC/MS). Ammonia and volatile sulfur compounds (VSCs) were the most abundant air pollutants, representing 55.5% and 20.6% of the cumulative mass emitted, respectively. The first eight days of aerobic treatment and the first turning of the compostable mixture were the critical steps for odor generation with OER ranging from 30 to 317 OUE h-1 kg-1ADS. Particularly, the first turning process was responsible for strong odor episodes that were emitted in a short process time (295 OUE h-1 kg-1ADS). Based on the OAVs approach, dimethyl disulfide, dimethyl sulfide, and methanethiol were the predominant odorants along these early operational stages. Odor potential and composition shifted for the middle and later active phase, second turning, and curing stage where OER fluctuated from 0.18 to 12.6 OUE h-1 kg-1ADS, and hydrogen sulfide showed the most substantial odor contribution. A principal component analysis explaining 77% of the variability in odor concentration and OAVs datasets eased the recognition of these odor patterns.

Intensification of volatile organic compound absorption in a compact wet scrubber at co-current flow.

Three volatile organic compounds (VOC) with no acidic or basic function (butanol, butyraldehyde, methylethylketone), encountered at low concentrations in odorous effluents, were absorbed in water in a compact wet scrubber. This gas-liquid contactor consisted of a wire mesh packing structure where the gas phase flows at high velocity (>12 m s-1). A very turbulent two-phase downward flow could be observed in the scrubber with dispersed fine droplets (around 10 µm). For compounds showing a good affinity for water, such as butanol, removal efficiencies up to 90% were measured for a short contactor length of 32 cm leading to a gas residence time of 20 ms. However, the removal efficiency of butyraldehyde, which is poorly soluble in water, ranged between 10 and 30%. Mass-transfer modeling was achieved and underlined that working with several small scrubbers in series, fed with an unloaded solution, is effective to improve the removal efficiency. The influences of the VOC/solvent affinity, the contactor length, and the mass-transfer and hydrodynamic parameters on the removal efficiency were evaluated through a sensitivity analysis.

A new combined green method for 2-Chlorophenol removal using cross-linked Brassica rapa peroxidase in silicone oil.

This study proposes a new technique to treat waste air containing 2-Chlorophenol (2-CP), namely an integrated process coupling absorption of the compound in an organic liquid phase and its enzymatic degradation. Silicone oil (47V20) was used as an organic absorbent to allow the volatile organic compound (VOC) transfer from the gas phase to the liquid phase followed by its degradation by means of Cross-linked Brassica rapa peroxidase (BRP) contained in the organic phase. An evaluation of silicone oil (47V20) absorption capacity towards 2-CP was first accomplished by determining its partition coefficient (H) in this solvent. The air-oil partition coefficient of 2-CP was found equal to 0.136 Pa m(3) mol(-1), which is five times lower than the air-water value (0.619 Pam(3) mol(-1)). The absorbed 2-CP was then subject to enzymatic degradation by cross-linked BRP aggregates (BRP-CLEAs). The degradation step was affected by four parameters (contact time; 2-CP, hydrogen peroxide and enzyme concentrations), which were optimized in order to obtain the highest conversion yield. A maximal conversion yield of 69% and a rate of 1.58 mg L(-1) min(-1)were obtained for 100 min duration time when 2-CP and hydrogen peroxide concentrations were respectively 80 mg L(-1) and 6 mM in the presence of 2.66 UI mL(-1) BRP-CLEAs. The reusability of BRP-CLEAs in silicone oil was assessed, showing promising results since 59% of their initial efficiency remained after three batches.

Biofiltration of high concentration of H2S in waste air under extreme acidic conditions.

Removal of high concentrations of hydrogen sulfide using a biofilter packed with expanded schist under extreme acidic conditions was performed. The impact of various parameters such as H2S concentration, pH changes and sulfate accumulation on the performances of the process was evaluated. Elimination efficiency decreased when the pH was lower than 1 and the sulfate accumulation was more than 12 mg S-SO4(2-)/g dry media, due to a continuous overloading by high H2S concentrations. The influence of these parameters on the degradation of H2S was clearly underlined, showing the need for their control, performed through an increase of watering flow rate. A maximum elimination capacity (ECmax) of 24.7 g m(-3) h(-1) was recorded. As a result, expanded schist represents an interesting packing material to remove high H2S concentration up to 360 ppmv with low pressure drops. In addition, experimental data were fitted using both Michaelis-Menten and Haldane models, showing that the Haldane model described more accurately experimental data since the inhibitory effect of H2S was taken into account.

Synthesis and toxicity evaluation of hydrophobic ionic liquids for volatile organic compounds biodegradation in a two-phase partitioning bioreactor.

Synthesis of several hydrophobic ionic liquids (ILs), which might be selected as good candidates for degradation of hydrophobic volatile organic compounds in a two-phase partitioning bioreactor (TPPB), were carried out. Several bioassays were also realized, such as toxicity evaluation on activated sludge and zebrafish, cytotoxicity, fluoride release in aqueous phase and biodegradability in order to verify their possible effects in case of discharge in the aquatic environment and/or human contact during industrial manipulation. The synthesized compounds consist of alkylimidazoliums, functionalized imidazoliums, isoqinoliniums, triazoliums, sulfoniums, pyrrolidiniums and morpholiniums and various counter-ions such as: PF6(-), NTf2(-) and NfO(-). Toxicity evaluation on activated sludge of each compound (5% v/v of IL) was assessed by using a glucose uptake inhibition test. Toxicity against zebrafish and cytotoxicity were evaluated by the ImPACCell platform of Rennes (France). Fluoride release in water was estimated by regular measurements using ion chromatography equipment. IL biodegradability was determined by measuring BOD28 of aqueous samples (compound concentration,1mM). All ILs tested were not biodegradable; while some of them were toxic toward activated sludge. Isoquinolinium ILs were toxic to human cancerous cell lines. Nevertheless no toxicity was found against zebrafish Danio rerio. Only one IL released fluoride after long-time agitation.

Intensification of volatile organic compounds mass transfer in a compact scrubber using the O3/H2O2 advanced oxidation process: kinetic study and hydroxyl radical tracking.

This study assesses the potential of ozonation and advanced oxidation process O(3)/H(2)O(2) to enhance the dimethyldisulfide (DMDS) mass transfer in a compact chemical scrubber developed for air treatment applications. Theoretical calculations, through Hatta number and enhancement factor evaluations for two parallel irreversible reactions, were compared to experimental data and enabled the description of the mass transfer mechanisms. These calculations required the determination of the kinetic constant of the DMDS oxidation by molecular ozone ( [Formula: see text] ) and the measurement of the hydroxyl radical concentration within the scrubber. The competitive kinetic method using the 1,2-dihydroxybenzene (resorcinol) enabled to determine a value of the kinetic constant [Formula: see text] of 1.1×10(6)M(-1)s(-1) at 293K. Then, experiments using para-chlorobenzoic acid in solution allowed measuring the average hydroxyl concentration in the scrubber between the inlet and the outlet depending on the chemical conditions (pH and inlet O(3) and H(2)O(2) concentrations). High hydroxyl radical concentrations (10(-8)M) and ratio of the HO°-to-O(3) exposure (R(ct)≈10(-4)) were put in evidence.

Ionic liquids: applications and future trends in bioreactor technology.

Ionic liquids (ILs) constitute a new generation of solvents entirely composed of ions. ILs are usually considered as green solvents due to their negligible vapor pressure and other properties, such as non-flammability and high thermostability. Biotechnological applications involving the use of ILs are currently emerging. Reports on enzymatic and whole-cell catalysis in the presence of ILs increased from the past decade. Nonetheless, IL decomposition at relatively low temperatures as well as IL toxicity towards microbial cells and superior organisms recently challenge the "green label" commonly attached to ILs. On the other hand, the possibility to fine-tune practically all the IL physicochemical properties by modifying its chemical structure makes IL truly designer solvents. Thus, IL tuning can be applied to overcome toxicity drawbacks and to broaden their application spectrum. This work reviews the use of ILs in biotechnological applications. Finally, critical niches for future research are identified and discussed.

Ozonation effect on natural organic matter adsorption and biodegradation--application to a membrane bioreactor containing activated carbon for drinking water production.

More stringent legislation on dissolved organic matter (DOM) urges the drinking water industry to improve in DOM removal, especially when applied to water with high dissolved organic carbon (DOC) contents and low turbidity. To improve conventional processes currently used in drinking water treatment plants (DWTPs), the performances of a hybrid membrane bioreactor containing fluidized activated carbon were investigated at the DWTP of Rennes. Preliminary results showed that the residual DOC was the major part of the non-biodegradable fraction. In order to increase the global efficiency, an upstream oxidation step was added to the process. Ozone was chosen to break large molecules and increase their biodegradability. The first step consisted of carrying out lab-scale experiments in order to optimise the necessary ozone dose by measuring the process yield, in terms of biodegradable dissolved organic carbon (BDOC). Secondly, activated carbon adsorption of the DOC present in ozonated water was quantified. The whole process was tested in a pilot unit under field conditions at the DWTP of Rennes (France). Lab-scale experiments confirmed that ozonation increases the BDOC fraction, reduces the aromaticity of the DOC and produces small size organic compounds. Adsorption tests led to the conclusion that activated carbon unexpectedly removes BDOC first. Finally, the pilot unit results revealed an additional BDOC removal (from 0.10 to 0.15 mg L(-1)) of dissolved organic carbon from the raw water considered.

Assessment and optimisation of VOC mass transfer enhancement by advanced oxidation process in a compact wet scrubber.

Dimethyl disulphide (DMDS) removal was investigated in a compact scrubber (hydraulic residence time approximately 20ms), composed of a wire mesh packing structure where liquid and gas flow at co-current and high gas superficial velocity (>12m s(-1)). In order to regenerate the scrubbing liquid and to maintain a driving force in the scrubber, ozone and hydrogen peroxide were added to water since they allow the generation of nonselective and highly reactive species, hydroxyl radicals HO(). Three ways of reagent distribution were tested. The influence of several parameters (liquid flow rate(s), ozone flow rate, pH and reagent concentrations) was investigated. The best configuration was obtained when ozone is transferred in the scrubbing liquid before introduction at the top of the scrubber simultaneously with the hydrogen peroxide solution, allowing to generate hydroxyl radical in the scrubber. With this configuration, DMDS removal could be increased from 16% with water to 34% at the same gas and liquid flow rates in the scrubber showing the potentiality of advanced oxidation process.