Defining the biomethane potential (BMP) of solid organic wastes and energy crops: a proposed protocol for batch assays.

The application of anaerobic digestion technology is growing worldwide because of its economic and environmental benefits. As a consequence, a number of studies and research activities dealing with the determination of the biogas potential of solid organic substrates have been carrying out in the recent years. Therefore, it is of particular importance to define a protocol for the determination of the ultimate methane potential for a given solid substrates. In fact, this parameter determines, to a certain extent, both design and economic details of a biogas plant. Furthermore, the definition of common units to be used in anaerobic assays is increasingly requested from the scientific and engineering community. This paper presents some guidelines for biomethane potential assays prepared by the Task Group for the Anaerobic Biodegradation, Activity and Inhibition Assays of the Anaerobic Digestion Specialist Group of the International Water Association. This is the first step for the definition of a standard protocol.

Energy potential of anaerobic digestion of solid wastes generated in the Russian Federation.

The well known use of the microbiological process of anaerobic digestion (AD) to generate biogas (mixture of methane and carbon dioxide) is now widely implemented for the production of renewable energy worldwide. In Russia, however, this is not the case despite huge amounts of solid organic wastes (SOW) suitable for AD. This paper firstly inventories major flows of SOW from various sectors of the national economy (agriculture, industry, households etc) and estimates their biogas potential. Special attention is put on existing bottlenecks and barriers to implementation of biogas technology given the Russian socio-economic conditions.

Development and optimisation of VFA driven DEAMOX process for treatment of strong nitrogenous anaerobic effluents.

The recently proposed DEAMOX (DEnitrifying AMmonium OXidation) process combines the anammox reaction with autotrophic denitrifying conditions using sulphide as an electron donor for the production of nitrite from nitrate within an anaerobic biofilm. This paper firstly presents a feasibility study of the DEAMOX process using synthetic (ammonia + nitrate) wastewater where sulphide is replaced by volatile fatty acids (VFA) as a more widespread electron donor for partial denitrification. Under the influent N-NH+4/N-NO3(-) and COD/N-NO3(-) ratios of 1 and 2.3, respectively, the typical efficiencies of ammonia removal were around 40% (no matter whether a VFA mixture or only acetate were used) for nitrogen loading rates (NLR) up to 1236 mg N/l/d. This parameter increased to 80% by increasing the influent COD/N-NO3(-) ratio to 3.48 and decreasing the influent N-NH4 +/N-NO3(-) ratio to 0.29. As a result, the total nitrogen removal increased to 95%. The proposed process was further tested with typical strong nitrogenous effluent such as reject water (total N, 530-566 mg N/l; total COD, 1530-1780 mg/l) after thermophilic sludge anaerobic digestion. For this, the raw wastewater was split and partially ( approximately 50%) fed to a nitrifying reactor (to generate nitrate) and the remaining part ( approximately 50%) was directed to the DEAMOX reactor where this stream was mixed with the nitrified effluent. Stable process performance up to NLR of 1,243 mg N/l/d in the DEAMOX reactor was achieved resulting in 40, 100, and 66% removal of ammonia, NOx(-), and total nitrogen, respectively.

New anaerobic process of nitrogen removal.

This paper reports on successful laboratory testing of a new nitrogen removal process called DEAMOX (DEnitrifying AMmonium OXidation) for the treatment of strong nitrogenous wastewater such as baker's yeast effluent. The concept of this process combines the recently discovered ANAMMOX (ANaerobic AMMonium OXidation) reaction with autotrophic denitrifying conditions using sulfide as an electron donor for the production of nitrite within an anaerobic biofilm. The achieved results with a nitrogen loading rate of higher than 1,000 mg/L/d and nitrogen removal of around 90% look very promising because they exceed (by 9-18 times) the corresponding nitrogen removal rates of conventional activated sludge systems. The paper describes also some characteristics of DEAMOX sludge, as well as the preliminary results of its microbiological characterization.

Kinetics of anaerobic biodecolourisation of azo dyes.

Kinetics of anaerobic biodecolourisation (methanogenic environment) of four azo dyes (Acid Orange 6, Acid Orange 7, Methyl Orange and Methyl Red) was investigated with regard to their electrochemical properties as well as under variation of dye and sludge concentrations, pH and temperature. Cyclic voltammetry revealed a correlation between the potential of irreversible reduction peak of the dye and its first-order decolorisation constant. For each dye tested, this decolourisation constant was adversely proportional to dye concentration (0.086-1.7 mM) and had a saturation (hyperbolic) dependency on sludge concentration (0.04-1.1 g VSS/l), a bell-shape dependency on pH (4.0-9.0) and Arrhenius dependency on temperature (24-40 degrees C). Transfer from methanogenic to sulphate reducing environment led to an increase of decolorisation constant for all the dyes investigated due to the abundant presence of sulphide as a reducing agent in the reaction medium. Similar transfer to a denitrifying environment resulted in an almost complete decease of decolourisation because nitrate easily outcompetes azo dyes as an electron acceptor.

Microbial conversion of selected azo dyes and their breakdown products.

Four selected azo dyes (acid orange 6, acid orange 7, methyl orange and methyl red) were completely decolourised in the presence of anaerobic granular sludge, while only methyl red was degraded in aerobic conditions using a conventional activated sludge. Additional experiments with culture broth devoid of cells showed that anaerobic decolourisation of azo dyes was performed by extracellular reducing agents produced by anaerobic bacteria. This was further confirmed by abiotic experiments with sulphide and NADH. The presence of redox mediators such as riboflavin led to dramatic acceleration of the anaerobic biodecolourisation process. The azo dye reduction products were found to be sulphanilic acid and 4-aminoresorcinol for acid orange 6; sulphanilic acid and 1-amino-2-naphthol for acid orange 7; N,N-dimethyl-1,4-phenylenediamine and sulphanilic acid for methyl orange; and N,N-dimethyl-1,4-phenylenediamine and anthranilic acid for methyl red. Anaerobic toxicity assays showed that the azo dyes were more toxic than their breakdown products (aromatic amines), except 1-amino-2-naphthol. In the presence of activated sludge, only anthranilic acid was completely mineralised while sulphanilic acid was persistent. 4-aminoresorcinol, 1-amino-2-naphthol and N,N-dimethyl-1,4-phenylenediamine underwent autooxidation in aerobic conditions yielding coloured polymeric products. On the contrary, in the presence of granular methanogenic sludge, 4-aminoresorcinol, 1-amino-2-naphthol and anthranilic acid were quantitatively methanised, sulphanilic acid was partially (70%) mineralised while N,N-dimethyl-1,4-phenylenediamine was only demethylated producing 1,4-phenylenediamine as an end product.

[Field-scale study on performance comparison of bio-augmentation and compost treatment of oily sludge].

In order to explore better treatment process of oily sludge, the field scale experiments were conducted using the sludge containing 12.68% oil. The performance of microbe preparation bio-augmentation (MPB) and compost treatment with manure (CTM) was compared. For the first experiment, 10 L solution containing 150 g microbe preparations and the nutrition were sprayed onto the MPBC cell. The initial oil content of final mixture amounted to 12.12%. The initial oil content of CTM after final mixture approximated to 10.14%. During the experimental period, same quantities of the microbe preparation and nutrient solution were sprayed on MPB at the 15th and 30th day separately. At the same days, the 10 kg manure was added to CTM cell. The degradation effect of MPB was more obvious, oil content dropped to 6.42% with a 47% removal rate of oil. The oil content in control decreased slightly to 10.15% after 56 days, while in CTM it fell down to 6.98% with a total removal rate of 31%. The pH in control fluctuated slightly between 8.28 to 7.93 while that in MPB, from 7.33 to 8.08, which might due to the addition of microbe preparation. The microbial count was analyzed weekly, which represented the adaptation ability of microbe in sludge. Temperature of compost increased rapidly up to 54 degrees C in the presence of manure. The differences of two kinds of methods were identified by GC-MS and the hydrocarbons with less 21 carbons were degraded easily.

Combined biological and physico-chemical treatment of baker's yeast wastewater.

The UASB reactor (35 degrees C) was quite efficient for removal of bulk COD (52-74%) from the raw and diluted cultivation medium from the first separation process of baker's yeasts (the average organic loading rates varied in the range 3.7-16 g COD/I/d). The aerobic-anoxic biofilter (19-23 degrees C) can be used for removal of remaining BOD and ammonia from anaerobic effluents; however, it had insufficient COD to fulfil the denitrification requirements. To balance COD/N ratio, some bypass of raw wastewater (approximately 10%) should be added to the biofilter feed. The application of iron (III)-, aluminium- or calcium-induced coagulation for post-treatment of aerobic effluents can fulfil the limits for discharge to sewerage (even for colour mainly exerted by hardly biodegradable melanoidins), however, the required amounts of coagulants were relatively high.

Integrated biological (anaerobic-aerobic) and physico-chemical treatment of baker's yeast wastewater.

The UASB reactor (35 degrees C) was quite efficient for removal of bulk COD (52-74%) from simulated (on the basis of cultivation medium from the first separation process) general effluent of baker's yeast production (the average organic loading rates varied from 8.1 to 16 g COD/l/d). The aerobic-anoxic biofilter (19-23 degrees C) can be used for removal of remaining BOD and ammonia from anaerobic effluents; however, it suffered from COD-deficiency to fulfil denitrification requirements. To balance COD/N ratio, some bypass (approximately 10%) of anaerobically untreated general effluent should be added to the biofilter feed. The application of iron (III)-, aluminium- or calcium-induced coagulation for post-treatment of aerobic-anoxic effluents can fulfil the limits for discharge to sewerage (even for colour mainly exerted by hardly biodegradable melanoidins), however, the required amounts of coagulants were relatively high.

Heavy metal pollution from Russian landfill leachates and its elimination together with other contaminants.

Systematic monitoring of raw leachates (RL) from the operating landfill "Khmet'yevo" during December, 2001--June, 2002 with regard to heavy metals (HM) revealed that these RL were moderately contaminated with Fe, Zn, Pb and Cd (Cu is present in non-dangerous concentrations). This contamination depends on season--the winter leachates are less polluted compared to the summer ones. For removal of HM together with removal of bulk COD, the UASB reactors were applied where, besides elimination of the major part of organic matter, concomitant precipitation of HM in the form of insoluble sulphides inside the sludge bed occurred due to development of the process of biological sulphate reduction. Both removal processes were quite efficient even during operation under submesophilic and psychrophilic conditions (20-10 degrees C). The subsequent submesophilic aerobic-anoxic treatment of submesophilic anaerobic effluents led to only 75% of total inorganic N removal due to COD deficiency for denitrification created by a too efficient anaerobic step. On the contrary, psychrophilic anaerobic effluents (richer in COD compared to the submesophilic ones) were more suitable for subsequent aerobic-anoxic treatment giving the total N removal of 95 and 92% at 20 and 10 degrees C, respectively. The final effluent is approaching the current national standards for direct discharge of treated wastewater.

Combined biological and physico-chemical treatment of baker's yeast wastewater including removal of coloured and recalcitrant to biodegradation pollutants.

The UASB reactor (35 degrees C) was quite efficient for removal of bulk COD (62-67%) even for such high strength and recalcitrant wastewater as the cultivation medium from the first separation process of baker'syeasts (the average organic loading rates varied from 3.7 to 10.3 g COD/l/d). The aerobic-anoxic biofilter (20 degrees C) can be used for removal of remaining BOD and ammonia from strong nitrogenous anaerobic effluents; however, it suffered from COD-deficiency to fulfil denitrification requirements. To balance the COD/N ratio, some bypass of raw wastewater should be added to the biofilter feed. The application of iron chloride coagulation for post-treatment of aerobic effluents may fulfil the discharge limits (even for colour mainly exerted by hardly biodegradable melanoidins) under iron concentrations around 200 mg/l.

Sequenced anaerobic-aerobic treatment of high strength, strong nitrogenous landfill leachates.

As a first step in treatment of high strength, strong nitrogenous landfill leachates (total COD--9.66-20.56 g/l, total nitrogen 780-1,080 mg/l), the performance of laboratory UASB reactors has been investigated under sub-mesophilic (19+/-3 degrees C) and psychrophilic (10+/-2 degrees C) conditions. Under hydraulic retention time (HRT) of around 1.2 days, when the average organic loading rate (OLR) was around 8.5 g COD/l/day, the total COD removal accounted for 71% (on average) for sub-mesophilic regime. The psychrophilic treatment conducted under the average HRT of 2.44 days and the average OLR of 4.2 g COD/l/day showed an average total COD removal of 58% giving effluents more suitable for subsequent biological nitrogen removal. Both anaerobic regimes were quite efficient for elimination of heavy metals by concomitant precipitation in the form of insoluble sulphides inside the sludge. The subsequent submesophilic aerobic-anoxic treatment of submesophilic anaerobic effluents led to only 75% of total inorganic N removal due to COD deficiency for denitrification created by too efficient anaerobic step. On the contrary, psychrophilic anaerobic effluents (richer in COD compared to the submesophilic ones) were more suitable for subsequent aerobic-anoxic treatment giving the total N removal of 95 and 92% at 19 and 10 degrees C, respectively.

Combined anaerobic-aerobic treatment of landfill leachates under mesophilic, submesophilic and psychrophilic conditions.

As a first step of treatment of landfill leachates (total COD--1,430-3,810 mg/l, total nitrogen 90-162 mg/l), a performance of laboratory UASB reactors has been investigated under mesophilic (30 degrees C), sub-mesophilic (20 degrees C) and psychrophilic (10 degrees C) conditions. Under hydraulic retention times (HRT) of around 7 h, when the average organic loading rates (OLR) were around 5 g COD/l/day, the total COD removal accounted for 81% (on the average) with the effluent concentrations close to anaerobic biodegradability limit (0.25 g COD/l) for mesophilic and sub-mesophilic regimes. The psychrophilic treatment conducted under the average HRT of 8 h and the average OLR of 4.22 g COD/l/day showed a total COD removal of 47% producing the effluents (0.75 g COD/l) more suitable for subsequent biological nitrogen removal. All three anaerobic regimes used for leachate treatment were quite efficient for elimination of heavy metals (Fe, Zn, Cu, Pb, Cd) by concomitant precipitation in the form of insoluble sulphides inside the sludge bed. The application of aerobic/anoxic biofilter as a sole polishing step for psychrophilic anaerobic effluents was acceptable for elimination of biodegradable COD and nitrogen approaching the current standards for direct discharge of treated wastewater.

Evaluation of the current status of operating and closed landfills in Russia, Finland and Ireland with regard to water pollution and methane emission.

The annual production of municipal solid wastes (MSW) in Russia, Finland and Ireland in the late 1990s accounts for 37.5, 2.5 and 2.05 min. tonnes or 252, 488 and 566 kg per capita, respectively. 96.5, 64 and 91% of these wastes (for Russia, Finland and Ireland, correspondingly) are currently disposed of via landfilling. However, nowadays, MSW management in these countries is undergoing drastic changes (source separation, closure of old landfills, reduction of the number of landfills etc.) forced by recent legislation set by the European Union and Russian authorities. This paper evaluates the current status of MSW landfills, as well as information on current leachate and methane emissions in the three above mentioned countries. Landfill leachates are highly variable in each country and between different countries due to different rainfall and climatic conditions and also due to poor landfill top insulation/cover. Leachates in poorly structured landfills are very dilute, whereas leachates with total COD and nitrogen contents as high as 33,700 mg COD/l and 4,030 mg N/l, respectively, have been detected from state-of-the-art sites. Currently, on-site treatment of leachates exists at only a few landfills in Russia, Finland and Ireland but this situation will be considerably improved during the next years. The annual methane emissions from landfills are estimated as 500-900 and 77 ktonnes for Russia and Finland, respectively. Recent estimates from Ireland suggest an annual landfill methane emission of c. 2.1 Mt CO2 equivalent. Several systems of methane recovery have been developed in all three countries and these are currently in different stages of implementation.

Combined biological and physico-chemical treatment of filtered pig manure wastewater: pilot investigations.

Combined biological and physico-chemical treatment of filtered pig manure wastewater has been investigated on the pilot installation operated under ambient temperatures (15-20 degrees C) and included: i) UASB-reactor for elimination of major part of COD from the filtrate; (ii) stripper of CO2 + fluidised bed crystallisator for phosphate (and partially ammonia) removal from the anaerobic effluents in the form of insoluble minerals-struvite (MgNH4PO4) and hydroxyapatite (Ca5(PO4)3OH); (iii) aerobic-anoxic biofilter for polishing the final effluent (elimination of remaining BOD and nutrients). Under overall hydraulic retention time (HRT) for the system of 7.8 days, the total COD, inorganic nitrogen and total phosphorous removals were 88, 65 and 74%, respectively. A decrease of the overall HRT to 4.25 days led to 91, 37 and 82% removals for total COD, inorganic nitrogen and total phosphorus removals, respectively. The approaches for further improvement of effluent quality are discussed.

The IWA Anaerobic Digestion Model No 1 (ADM1).

The IWA Anaerobic Digestion Modelling Task Group was established in 1997 at the 8th World Congress on Anaerobic Digestion (Sendai, Japan) with the goal of developing a generalised anaerobic digestion model. The structured model includes multiple steps describing biochemical as well as physicochemical processes. The biochemical steps include disintegration from homogeneous particulates to carbohydrates, proteins and lipids; extracellular hydrolysis of these particulate substrates to sugars, amino acids, and long chain fatty acids (LCFA), respectively; acidogenesis from sugars and amino acids to volatile fatty acids (VFAs) and hydrogen; acetogenesis of LCFA and VFAs to acetate; and separate methanogenesis steps from acetate and hydrogen/CO2. The physico-chemical equations describe ion association and dissociation, and gas-liquid transfer. Implemented as a differential and algebraic equation (DAE) set, there are 26 dynamic state concentration variables, and 8 implicit algebraic variables per reactor vessel or element. Implemented as differential equations (DE) only, there are 32 dynamic concentration state variables.

Psychrophilic one- and two-step systems for pre-treatment of winery waste water.

The operation performance of a single and two (in series) laboratory UASB reactors (working volume of 2.7 l, recycle ratio varied from 1:1 to 1:18) treating diluted wine vinasse was investigated under psychrophilic conditions (4-10 degrees C). For a single UASB reactor seeded with granular sludge, the average organic loading rates (OLR) applied were 4.7, 3.7 and 1.7 g COD/l/d (hydraulic retention times (HRTs) were around 1 d) at 9-11, 6-7 and 4-5 degrees C, respectively. The average total COD removal for preacidified vinasse wastewater was around 60% for all the temperature regimes tested. For two UASB reactors in series, the average total COD removal for treatment of non-preacidified wastewater exceeded 70% (the average OLRs for a whole system were 2.2, 1.8 and 1.3 g COD/l/d under HRTs of 2 days at 10, 7 and 4 degrees C, respectively). In situ determinations of kinetic sludge characteristics (Vm and Km) revealed the existence of substantial mass-transfer limitations for the soluble substrates inside the reactor sludge bed. Therefore an application of higher recycle rations is essential for enhancement of UASB pre-treatment under psychrophilic conditions. The produced anaerobic effluents were shown to be efficiently post-treated aerobically--final effluent COD concentrations were around 0.1 g/l.

One- and two-stage upflow anaerobic sludge-bed reactor pretreatment of winery wastewater at 4-10 degreesC.

The operating performance of a single and two (in series) laboratory upflow anaerobic sludge-bed (UASB) reactors (2.7-L working volume, recycle ratio varied from 1:1 to 1:18) treating diluted wine vinasse was investigated under psychrophilic conditions (4-10 degreesC). For a single UASB reactor seeded with granular sludge, the average organic loading rates (OLRs) applied were 4.7, 3.7, and 1.7 g of chemical oxygen demand (COD)/(L.d) (hydraulic retention times [HRTs] were about 1 d) at 9-11, 6 to 7, and 4 to 5 degreesC, respectively. The average total COD removal for preacidified vinasse wastewater was about 60% for all the temperature regimes tested. For two UASB reactors in series, the average total COD removal for treatment of non-preacidified wastewater exceeded 70% (the average OLRs for a whole system were 2.2, 1.8, and 1.3 g of COD/[L.d] under HRTs of 2 d at 10, 7, and 4 degreesC, respectively). In situ determinations of kinetic sludge characteristics (apparent Vm and Km) revealed the existence of substantial mass transfer limitations for the soluble substrates inside the reactor sludge bed. Therefore, application of higher recycle ratios is essential for enhancement of UASB pretreatment under psychrophilic conditions. The produced anaerobic effluents were shown to be efficiently posttreated aerobically: final effluent COD concentrations were about 0.1 g/L. Successful operation of the UASB reactors at quite low temperatures (4-10 degreesC) opens some perspectives for application of high-rate anaerobic pretreatment at ambient temperatures.

Bioremediation of oil polluted aquatic systems and soils with novel preparation 'Rhoder'.

This paper summarises the experience accumulated during the field application of biopreparation 'Rhoder' (solely or in a combination with preliminary mechanical collection of free oil) for remediation of oil polluted aquatic systems and soils in the Moscow region and Western Siberia during 1994-1999. It was demonstrated that 'Rhoder' had a very high efficiency (>99%) for bioremediation of the open aquatic surfaces (100 m2 bay of the River Chernaya, two 5,000 m2 lakes in Vyngayakha) at initial level of oil pollution of 0.4-19.1 g/l. During remediation of the wetland (2,000 m2) in Urai (initial level of oil pollution of 10.5 g/l), a preliminary mechanical collection of oil was applied (75% removal) followed by a triple treatment with 'Rhoder'. It resulted in an overall treatment efficiency of 94%. Relatively inferior results of bioremediation of the 10,000 m2 wetland in Vyngayakha (65% removal) and the 1,000 m2 marshy peat soil in Nizhnevartovsk (19% removal) can be attributed to the very high initial level of oil pollution (24.3 g/l and >750 g/g dry matter, respectively) aggravated by the fact that it was impossible to apply a preliminary mechanical collection of oil on these sites. A possible strategy for remediation of such heavily polluted sites is discussed.

Two-particle model of anaerobic solid state fermentation.

A structured mathematical model of anaerobic solid state fermentation (ASSF) has been developed. Since a stable ASSF requires addition of significant quantities of methanogenic seed sludge and mass-transfer limitation becomes important, the model postulates the existence of two different types of particles inside the fermenting solid mass--so-called "seed" particles with low biodegradability and high methanogenic activity and so-called "waste" particles with high biodegradability and low methanogenic activity. Any particle is assumed to be a completely mixed reactor and mass transfer of solutes between the particles is brought about by diffusion. The model includes multiple-reaction stoichiometry, microbial growth kinetics, material balances, liquid-gas interactions and liquid phase equilibrium chemistry. The theoretical model agrees on the qualitative level with existing experimental studies of ASSF. Hypothetical computer simulations are presented to illustrate the influence of biodegradability and mass transfer intensity on the stability of ASSF. On this basis, possible measures are proposed to prevent accumulation of volatile fatty acids inside the "seed" particles beyond their assimilative methanogenic capacity.