Olive mill wastes: from wastes to resources.

Olive oil extraction has recently experienced a continuous increase due to its related beneficial properties. Consequently, large amounts of olive mill wastes (OMWs) derived from the trituration process are annually produced, causing serious environmental problems. The limited financial capabilities of olive mills make them usually unable to bear the high costs required for the disposal of their wastes. Alternatively, the valorization of OMWs within the framework of the so-called waste-to-resource concept and their recycling can represent a successful strategy for the implementation of circular economy model in the olive industry, which could have significant socioeconomic impacts on low-income Mediterranean countries. There is, however, no unique solution for OMWs valorization, due to the wide variety of the wastes' composition and their seasonal production. In this review, the potential of OMWs for being reused and the recent technological advances in the field of OMWs valorization are assessed. Special focus is given to the analysis of the advantages and limitations of each technology and to reporting the most significant issues that still limiting its industrial scale-up. The information collected in this review shows that OMW could be effectively exploited in several sectors, including energy production and agriculture. OMWs potential seems, however, undervalued, and the implementation of sustainable valorization strategies in large-scale remains challenging. More efforts and policy actions, through collective actions, encouraging subsidies, and establishing public-private collaborations, are still needed to reconcile research progress with industrial practices and encourage the large-scale implementation of the waste-to-resource concept in the olive sector.

Anaerobic digestibility of aerobic granular sludge from continuous flow reactors: the role of granule size distribution.

There is an increasing interest in integrating aerobic granular sludge (AGS) technology into wastewater industries. Several projects are being performed to cultivate the aerobic granules for continuous flow reactors (AGS-CFR), while there is a scarcity of those projects that investigate the bio-energy recovery from AGS-CFR. This research was designed to examine the digestibility of AGS-CFR. Beyond that, it aimed at defining the role of the granule size on their digestibility. For this purpose, a series of bio-methane potential (BMP) tests have been run at mesophilic conditions. The results showed that AGS-CFR has a lower methane potential (107.43 ± 4.30 NmL/g VS) compared to activated sludge. This may be the result of the high sludge age (30 days) of AGS-CFR. Additionally, the results revealed that the average size of granules is among the main factors that reduce their digestibility, but it does not inhibit it. It was noticed that granules of size >250 µm have a significantly lower methane yield than the smaller ones. Kinetically, it was noticed that the kinetic models with two hydrolysis rates fit well with the methane curve of AGS-CFR. Overall, this work showed that the average size of AGS-CFR characterizes its biodegradability, which in turn defines its methane yield.

Hydraulic modeling of a compact stormwater treatment device applying concepts of dynamic similitude.

The development of compact treatment devices (CTDs) with high removal efficiencies and low space requirements is a key objective of urban stormwater treatment. Thus, many devices utilize a combination of sedimentation and upward-flow filtration in a single system. Here, sedimentation is used before filtration, which makes it difficult to evaluate the individual treatment stages separately. This study determines the removal efficiency by sedimentation and the expected filter load in a specific compact treatment device designed for a catchment area of up to 10,000 m2. In contrast to a full-scale investigation, small-scale physical hydraulic modeling is applied as a new cost-saving alternative. To validate upscaling laws, tracer signals and particle-size-specific removal efficiencies are determined for two geometrically similar models at different length scales. Thereby, Reynolds number similarity produces similar flow patterns, while the similarity of Hazen numbers allows to upscale removal efficiencies. Upscaling to the full-scale reveals that the filter in the device is only partly loaded by particulate matter that consists mostly of particles ≤63 µm. Thus, sedimentation upstream of a filter is of relevant importance in CTDs. The proposed dimensionless relationship may be used for particles from different catchments and helps to size the device accordingly.

Design-oriented evaluation of the hydrodynamics in a full-scale combined filter-lamella separator for urban stormwater treatment.

The development of compact treatment devices with high removal efficiencies and low space requirements is a key objective of urban stormwater treatment. Thus, many devices utilize a combination of sedimentation and upward flow filtration in a single system. This study, for the first time, evaluates the flow field inside a combined filter-lamella separator via computational fluid dynamics. Herein, three objectives are investigated: (i) the flow field for different structural configurations, (ii) the distribution of particulate matter along the filter bed and (iii) the dynamic clogging in discrete filter zones, which is addressed by a clogging model derived from literature data. The results indicate that a direct combination of a filtration stage with a lamella separator promotes a uniform flow distribution. The distribution of particulate matter along the filter bed varies with configuration and particle size. Clogging, induced by particles in the spectrum <63 µm, creates gradients of hydraulic conductivity along the filter bed. After treating about half of Germany's annual runoff-efficient precipitation at a rainfall intensity of 5 L/(s·ha), the filtration rates increase in the front of the filter bed by +10%. Thus, long-term operating behavior is sensitive to efficient filter utilization in compact treatment devices.

Slow sand filtration of raw wastewater using biochar as an alternative filtration media.

The efficiency of anaerobic biofilters (AnBF) as low-cost wastewater treatment systems was investigated. Miscanthus-biochar was used as filtration media and compared with sand as a common reference material. Raw sewage from a municipal wastewater treatment plant was stored in a sedimentation tank for two days to allow pre-settlement of wastewater particles. Subsequently, wastewater was treated by AnBFs at 22 °C room temperature at a hydraulic loading rate of 0.05 m∙h-1 with an empty bed contact time of 14.4 h and a mean organic loading rate of 509 ± 173 gCOD∙m-3∙d-1. Mean removal of chemical oxygen demand (COD) of biochar filters was with 74 ± 18% significantly higher than of sand filters (61 ± 12%). In contrast to sand filters with a mean reduction of 1.18 ± 0.31 log-units, E. coli removal through biochar was with 1.35 ± 0.27 log-units significantly higher and increased with experimental time. Main removal took place within the schmutzdecke, a biologically active dirt layer that develops simultaneously on the surface of filter beds. Since the E. coli contamination of both filter materials was equal, the higher removal efficiency of biochar filters is probably a result of an improved biodegradation within deeper zones of the filter bed. Overall, performance of biochar filters was better or equal compared to sand and have thus demonstrated the suitability of Miscanthus-biochar as filter media for wastewater treatment.

Phytotoxicity assessment of olive mill wastewater treated by different technologies: effect on seed germination of maize and tomato.

The phytotoxicity effect of olive mill wastewater (OMWW) treated in a combined system regrouping pretreatment by filtration on olive stones and coagulation-flocculation, and anaerobic digestion (AD) on seed germination of maize and tomato was evaluated through germination tests in petri dishes and growth tests in pots. Three samples, referenced as AD-40, AD-60, and AD-80, were collected from the anaerobic reactor operating with an influent at 40, 60, and 80% OMWW/water (% v/v). Concentrations between 25 and 100% were used for maize and between 5 and 25% were used for tomato using raw and pretreated samples, while anaerobic samples were used without dilution. For maize, 100% and 75% OMWW were very phytotoxic and completely prohibited seed germination, while phytotoxicity was decreased following dilution at 25% and 50% OMWW. Maize germinability was found highly enhanced when watered with anaerobic samples. For tomato, high dilution was required to reduce the phytotoxicity of raw and pretreated OMWW and a high relative germination percentage was registered at 5, 10, and 15% OMWW, while for samples anaerobically treated, a high phytotoxicity is still observed. Growth tests, showed more favorable results for maize watered with raw and pretreated samples at 25% OMWW and with biological samples. For tomato and with the exception of 25% OMWW and AD-80, seeds respond positively to all samples. It was concluded that if the OMWW will be used for irrigating maize, it could be directly used after anaerobic digestion, while for tomato further dilution is required. The phenolic profile analysis of the tested samples coupled with the results of the germination tests showed that the OMWW phytotoxicity appears to be determined by not only the monomeric phenols but also by other toxic components unaffected by the applied treatments.

Packed-bed biofilm reactor for semi-continuous anaerobic digestion of olive mill wastewater: performances and COD mass balance analysis.

In the present study, the treatability of olive mill wastewater (OMWW) using an anaerobic fixed bed biofilm reactor packed with granular activated carbon (GAC) and inoculated with non-acclimated biomass was performed in a semi-continuous mode under mesophilic conditions. Three organic loading rates (OLR) varied from 0.94 to 2.81 g COD/(L d) were applied. The results of batch adsorption tests on GAC and the experimental data from PBBR-GAC operation were used to set up a COD mass balance in order to investigate the effect of adsorption on the COD removal during the three anaerobic treatment steps. Despite the slight accumulation of volatile fatty acids (VFAs) during the second and the third steps, between 735 and 1135 mg COD/L (as acetic acid), a stable environment for methanogens was maintained for a period of 104 days. During the three steps, degradation levels were up to 80% of COD and 85% of phenolic compounds. An averaged specific biogas production of 1.77 LN/d and a methane (CH4) concentration of about 60%, corresponding to a CH4 yield of 0.31 L CH4produced/g CODdepleted, were reached at an OLR of 2.81 g COD/(L d). The results show that the COD mass balance was not closed during the first two steps, while in the third step, it could be around 96%. This finding suggests that the adsorption of organic substances on activated carbon occur just during the two first steps, while at 2.81 g COD/(L d) OLR no adsorption is occurring and the introduced COD becomes completely available for CH4 production.

Performance and inorganic fouling of a submergible 255 L prototype microbial fuel cell module during continuous long-term operation with real municipal wastewater under practical conditions.

A submergible 255 L prototype MFC module was operated under practical conditions with municipal wastewater having a large share in industrial discharges for 98 days to investigate the performance of two of the largest, ever investigated multi-panel stainless steel/activated carbon air cathodes (85 × 85 cm). At a flow rate of 144 L/d, power density of 78 mW/m2Cat (317 mW/m3) and COD, TSS and TN removal of 41 ±â€¯16 %, 36 ±â€¯16 % and 18 ±â€¯14 %, respectively, were reached. Observed Coulombic efficiency and substrate-specific energy recovery were 29.5 ±â€¯14 % and 0.184 ±â€¯0.125 kWhel/kgCOD,deg, respectively. High salt content of wastewater (TDS = 2.8 g/L) led to severe inorganic fouling causing a drastic decline in power output and energy recovery of more than 90 % in the course of experiments. Mechanical cleaning of the cathodes restored only 22 % (17 mW/m2Cat) of the power output and did not improve nutrient removal or energy recovery.

On-farm wastewater treatment using biochar from local agroresidues reduces pathogens from irrigation water for safer food production in developing countries.

In this study, the suitability of an anaerobic biofilter (AnBF) as an efficient and low-cost wastewater treatment for safer irrigation water production for Sub-Saharan Africa was investigated. To determine the influence of different ubiquitous available materials on the treatment efficiency of the AnBF, rice husks and their pyrolysed equivalent, rice husk biochar, were used as filtration media and compared with sand as a common reference material. Raw sewage from a municipal full-scale wastewater treatment plant pretreated with an anaerobic filter (AF) was used in this experiment. The filters were operated at 22 °C room temperature with a hydraulic loading rate of 0.05 m·h-1 for 400 days. The mean organic loading rate (OLR) of the AF was 194 ±â€¯74 and 63 ±â€¯16 gCOD·m-3·d-1 for the AnBF. Fecal indicator bacteria (FIB) (up to 3.9 log10-units), bacteriophages (up to 2.7 log10-units), chemical oxygen demand (COD) (up to 94%) and turbidity (up to 97%) could be significantly reduced. Additionally, the essential plant nutrients nitrogen and phosphorous were not significantly affected by the water treatment. Overall, the performance of the biochar filters was significantly better than or equal to the sand and rice husk filters. By using the treated wastewater for irrigating lettuce plants in a pot experiment, the contamination with FIB was >2.5 log-units lower (for most of the plants below the detection limit of 5.6 MPN per gram fresh weight) than for plants irrigated with raw wastewater. Respective soil samples were minimally contaminated and nearly in the same range as that of tap water.

Assessing potential impacts of phosphate precipitation on nitrous oxide emissions and the carbon footprint of wastewater treatment plants.

Metal salts are widely used for the precipitation of phosphorus during wastewater treatment transforming soluble orthophosphate to an insoluble salt. In practice, more complex reactions are taking place including a reduction of the chemical solubility of dissolved greenhouse gases, such as nitrous oxide, present in the wastewater stream. In this respect, it was postulated that phosphorous precipitation will lead to artificial N2O stripping and hence to an increased carbon footprint of wastewater treatment plants. From lab-scale experiments utilizing N2O-saturated synthetic sewage solutions, it was evidenced that metal salt addition leads to N2O stripping with 20.8 g N2O per liter for a FeCl2-based precipitant to 26.4 g N2O per liter for a Aln(OH)mCl3n-m-based precipitant. Taking this maximum potential stripping effect into account for a carbon footprint analysis, a potential contribution of 16.11 kg CO2,eq·PE-1·a-1 was calculated in a case study, where FeCl3 was considered. With respect to the defined system boundary conditions, the overall on-site and off-site CO2 emissions were raised by 34% from 46.87 kg CO2,eq·PE-1·a-1 to 62.97 kg CO2,eq·PE-1·a-1 through CO2,eq coming from phosphorous precipitation.

Olive mill wastewater pretreatment by combination of filtration on olive stone filters and coagulation-flocculation.

In the present study a new combined process, comprising filtration of raw olive mill wastewater (OMWW) on two successive olive stone (OS) filters followed by a coagulation-flocculation, was developed in order to perform an efficient pretreatment of OMWW. The results show that the use of OS filter leads to a higher removal of total suspended solids (TSS) and fatty matter (FM) from the raw OMWW (about 82.5% and 73.8%, respectively) and a depletion of total phenolic compounds (TP) and chemical oxygen demand (COD) (11.3% and 23.2%, respectively). The coagulation-flocculation was then applied to improve the removal of TP and COD from the filtered OMWW. For this purpose, a full-factorial design was used to study the effect of different factors involved in coagulation-flocculation. The studied variables were: pH (5-8), coagulant type (ferric chloride; FC and aluminum sulfate; AS), coagulant concentration (250-1000 mg/L) and flocculant (Anionique polyelectrolyte Superfloc A120 PWG) concentration (1-5 mg/L). The results reveal that the use of 250 mg/L FC and 5 mg/L flocculant at an acid pH (around 5) allows for, respectively, a removal of TP and COD of about 10.8% and 31.3%.

Development of an Extended ASM3 Model for Predicting the Nitrous Oxide Emissions in a Full-Scale Wastewater Treatment Plant.

An Activated Sludge Model #3 (ASM3) based, pseudomechanistic model describing nitrous oxide (N2O) production was created in this study to provide more insight into the dynamics of N2O production, consumption, and emissions at a full-scale wastewater treatment plant (WWTP). N2O emissions at the studied WWTP are monitored throughout the plant with a Fourier transform infrared analyzer, while the developed model encountered N2O production in the biological reactors via both ammonia oxidizing bacteria (AOB) nitrification and heterotrophic denitrifiers. Additionally, the stripping of N2O was included by applying a KL a-based approach that has not been widely used before. The objective was to extend the existing ASM3-based model of the plant and assess how well the full-scale emissions could be predicted with the selected model. The validity and applicability of the model were tested by comparing the simulation results with the comprehensive online data. The results show that the ASM3-based model can be successfully extended and applied to modeling N2O production and emissions at a full-scale WWTP. These results demonstrate that the biological reactor can explain most of the N2O emissions at the plant, but a significant proportion of the liquid-phase N2O is further transferred during the process.

Quantifying direct carbon dioxide emissions from wastewater treatment units by nondispersive infrared sensor (NDIR) - A pilot study.

Treatment of nutrient-rich wastewater potentially results in direct release of greenhouse gases (GHGs) such as CO2, N2O or CH4 - and thus affects Waste Water Treatment Plant's carbon footprint. Accurate CO2 quantification is challenging due to various chemical, physical and operational conditions. A floating chamber equipped with a nondispersive infrared, single beam, dual wavelength sensor has been evaluated for a pilot approach to quantify fugitive CO2 emissions above different wastewater treatment units. Total average CO2 flux was 1182gCO2·m-2·d-1 with minimum and maximum fluxes of 829gCO2·m-2·d-1 and 1493gCO2·m-2·d-1, respectively. Total observed CO2 emissions were in 7 to 17kgCO2·PE-1·a-1 (average 12kgCO2·PE-1·a-1). The nitrification tank accounted for about 94.3% of the emissions, followed by secondary clarification (ca. 4.3%) and denitrification (ca. 1.4%), based on those average annual CO2 emissions per population equivalent (PE).

Inhibition of microbial fuel cell operation for municipal wastewater treatment by impact loads of free ammonia in bench- and 45L-scale.

A 45-liter microbial fuel cell (MFC) system was integrated into a full-scale wastewater treatment plant (WWTP). The system was operated under practical conditions with supernatant of a pre-thickener for 50days in order to identify, whether higher power output and energy recovery is possible compared to the use of primary clarifier effluent, as used in a previous study. The higher COD (chemical oxygen demand) loading rates of supernatant neither increased power densities, nor energy recovery, but impact loads of total ammonia nitrogen (TAN) in concentrations >800mg/L (free ammonia nitrogen (FAN)>40mg/L) led to an instant collapse of power output and nutrient removal, which was reversed when ammonia concentrations decreased. Investigations in lab-scale under defined conditions verified that the inhibition of the exoelectrogenic biofilm is in fact caused by high levels of FAN. Here, COD removal, power output and energy recovery constantly decreased, when FAN-concentrations were increased above 64mg/L.

Quantification of nitrous oxide in wastewater based on salt-induced stripping.

Monitoring nitrous oxide (N2O) emissions from wastewater treatment plants has attracted much attention in recent years demanding accurate and rapid quantification methods. In the present study a salt-assisted methodology is proposed by which N2O is chemically stripped out from wastewater and quantified by gas chromatography (GC-TCD) subsequently. Eight different inorganic salts have been evaluated for this purpose, likewise the application of ultrasound. By addition of sodium bromide (NaBr) the best recovery rate of about 98% (=1.14±0.05kg·m-3) N2O from a saturated stock solution (1.16kg·m-3, 295.85K and 1atm) was achieved. The application of ultrasound led to considerable smaller N2O recoveries of 37% (=0.43±0.01kg·m-3) after a 60min treatment. Practical applicability of the method has been demonstrated by applying NaBr to grab samples from a municipal wastewater treatment plant. The highest N2O concentration was found in the secondary clarifier with 10.99±0.20g·m-3. Besides, N2O could be quantified in the activated sludge process with up to 9.87±0.50g·m-3 yielding 7.75gN2O·PE-1·a-1 specifically for the investigated wastewater treatment plant. Hence, the proposed method proved suitable as a routine quantification method for N2O.

Determination of the fractions of syntrophically oxidized acetate in a mesophilic methanogenic reactor through an (12)C and (13)C isotope-based kinetic model.

In order to accurately describe the carbon flow in anaerobic digestion processes, this work investigates the acetate degradation pathways through the use of stable carbon isotope analysis and a mathematical model. Batch assays using labeled (13)C acetate were employed to distinguish the acetate consumption through methanogenic Archaea and acetate-oxidizing Bacteria. Suspended and sessile biomass, with over 400 days of retention time, from a mesophilic (36.5 °C) upflow anaerobic filter was used as inocula in these assays. A three-process model for acetoclastic methanogenesis and syntrophic acetate oxidation (SAO) was developed to allow for a precise quantification of the SAO contribution. The model distinguishes carbon atoms in light and heavy isotopes, (12)C and (13)C, respectively, which permitted the simulation of the isotope ratios variation in addition to gas production, gas composition and acetate concentrations. The model indicated oxidized fractions of acetate between 7 and 18%. Due to the low free ammonia inhibition potential for the acetoclastic methanogens in these assays these findings point to the biomass retention times as a driven factor for the SAO pathway. The isotope-based kinetic model developed here also describes the δ(13)C variations in unlabeled assays accurately and has the potential to determine biological (13)C fractionation factors.

An integrated 45L pilot microbial fuel cell system at a full-scale wastewater treatment plant.

A 45-L pilot MFC system, consisting of four single-chamber membraneless MFCs, was integrated into a full-scale wastewater treatment plant (WWTP) and operated under practical conditions with the effluent of the primary clarifier for nine months to identify an optimal operational strategy for stable power output and maximum substrate based energy recovery (Normalized Energy Recovery, NER). Best results with the MFC were obtained at a hydraulic retention time of 22h with COD, TSS and nitrogen removal of 24%, 40% and 28%, respectively. Mean NER of 0.36kWhel/kgCOD,deg and coulombic efficiency of 24.8% were reached. Experimental results were used to set up the first described energy balance for a whole WWTP with an integrated MFC system. Energetic calculations of the model WWTP showed that energy savings due to reduced excess sludge production and energy gain of the MFC are significantly higher than the loss of energy due to reduced biogas production.

Influent Fractionation for Modeling Continuous Anaerobic Digestion Processes.

The first dynamic model developed to describe anaerobic digestion processes dates back to 1969. Since then, considerable improvements in identifying the underlying biochemical processes and associated microorganisms have been achieved. These have led to an increasing complexity of both model structure and the standard set of stoichiometric and kinetic parameters. Literature has always paid attention to kinetic parameter estimation, as this determines model accuracy with respect to predicting the dynamic behavior of biogas systems. As sufficient computing power is easily available nowadays, sophisticated linear and nonlinear parameter estimation techniques are applied to evaluate parameter uncertainty. However, the uncertainty of influent fractionation in these parameter optimization procedures is generally neglected. As anaerobic digestion systems are currently increasingly used to convert a broad variety of organic biomass to methane, the lack of generally accepted guidelines for input characterization adapted to the simulation model's characteristics is a considerable limitation of model application to these substrates. Directly after the introduction of the standardized Anaerobic Digestion Model No. 1 (ADM1), several publications pointed out that the model's requirement of a detailed influent characterization can hardly be fulfilled. The main shortcoming of the model application was addressed in the reliable and practical identification of the model's input state variables for particulate and soluble carbohydrates, proteins and lipids, as well as for the inerts. Several authors derived biomass characterization procedures, most of them dedicated to a particular substrate, and some of them being of general nature, but none of these approaches have resulted in a practical standard protocol so far. This review provides an overview of existing approaches that improve substrate influent characterization to be used for state of the art anaerobic digestion models.

Determination of methanogenic pathways through carbon isotope (δ13C) analysis for the two-stage anaerobic digestion of high-solids substrates.

This study used carbon isotope (δ(13)C)-based calculations to quantify the specific methanogenic pathways in a two-stage experimental biogas plant composed of three thermophilic leach bed reactors (51-56 °C) followed by a mesophilic (36.5 °C) anaerobic filter. Despite the continuous dominance of the acetoclastic Methanosaeta in the anaerobic filter, the methane (CH4) fraction derived from carbon dioxide reduction (CO2), fmc, varied significantly over the investigation period of 200 days. At organic loading rates (OLRs) below 6.0 gCOD L(-1) d(-1), the average fmc value was 33%, whereas at higher OLRs, with a maximum level of 17.0 gCOD L(-1) d(-1), the fmc values reached 47%. The experiments allowed for a clear differentiation of the isotope fractionation related to the formation and consumption of acetate in both stages of the plant. Our data indicate constant carbon isotope fractionation for acetate formation at different OLRs within the thermophilic leach bed reactors as well as a negligible contribution of homoacetogenesis. These results present the first quantification of methanogenic pathway (fmc values) dynamics for a continually operated mesophilic bioreactor and highlight the enormous potential of δ(13)C analysis for a more comprehensive understanding of the anaerobic degradation processes in CH4-producing biogas plants.

Biogas from grass silage - Measurements and modeling with ADM1.

Mono fermentation of grass silage without the addition of manure was performed over a period of 345days under mesophilic conditions (38 degrees C). A simulation study based on the IWA Anaerobic Digestion Model No. 1 (ADM1) was done in order to show its applicability to lignocellulosic biomass. Therefore, the influent was fractioned by established fodder analysis (Weender analysis and van Soest method). ADM1 was modified with a separate compound of inert decay products similar to the approach of Activated Sludge Model No. 1 (ASM1). Furthermore, a function, which described the influence of solids on the process of hydrolysis, has been integrated to reproduce reliable ammonium concentrations. The model was calibrated by using the modified Nash-Sutcliffe coefficient to evaluate simulation quality. It was possible to fit observed data by changing only hydrogen inhibition constants and the maximum acetate uptake rate. The extended ADM1 model showed good agreement with measurements and was suitable for modeling anaerobic digestion of grass silage.