Stephan Tait

Estimation of hydrolysis parameters in full‐scale anerobic digesters

In hydrolysis-limited anerobic systems, the key parameters describing degradation are degradability extent (f(d)), and the lumped apparent first order coefficient (k(hyd)). These are often measured in biological methane potential (BMP) tests. Using modern techniques, it should also be possible to estimate these parameters in full-scale systems, especially where inputs are dynamic. In this study, we evaluated f(d) and k(hyd) values and uncertainty based on nonlinear parameter estimation from (i) BMP tests and (ii) effluent gas and solids from two full-scale digesters fed with highly variable feed flows and concentrations (up to 6 kg COD m(-3) day(-1)). The substrate was thermally hydrolyzed activated sludge, and the inoculum for BMP tests was from the full-scale digesters. While identifiability of both parameters in the BMP tests was generally good, only f(d) could be well identified using continuous data. For k(hyd) using continuous data, normally only a lower limit could be found (upper was unbounded). In addition, parameters as estimated on different outputs (VS and gasflow) and two different digesters were consistent, with an f(d) value of 0.45-0.55, and a k(hyd) value of >5 day(-1). Gradual changes in f(d) over the 450 days could be related to upstream changes. f(d) values as estimated in BMP tests were consistent (if conservative) with continuous estimates, with a f(d) in BMP of 0.4-0.5. k(hyd) values were an order of magnitude lower (0.15-0.25 day(-1) vs. >5 day(-1)), and this translated to very poor model performance when BMP-estimated values were used in the continuous model. This means that while BMP testing may be used for project feasibility analysis, values obtained should not be used for dynamic modeling. The parameter confidence regions found were highly nonlinear, especially for continuous systems, indicating that iterative or sampling techniques are required for an estimate of real parameter uncertainty.

Decreasing activated sludge thermal hydrolysis temperature reduces product colour, without decreasing degradability

Activated sludges are becoming more difficult to degrade in anaerobic digesters, due to the implementation of stricter nitrogen limits, longer sludge ages, and removal of primary sedimentation units. Thermal hydrolysis is a popular method to enhance degradability of long-age activated sludge, and involves pressure and heat treatment of the process fluid (150-160 degrees C saturated steam). However, as documented in this study, in a full-scale system, the use of thermal hydrolysis produces coloured, recalcitrant compounds that can have downstream impacts (e.g., failure of UV disinfection, and increased effluent nitrogen). The coloured compound formed during thermal hydrolysis was found to be melanoidins. These are coloured recalcitrant compounds produced by polymerisation of low molecular weight intermediates, such as carbohydrates and amino compounds at elevated temperature (Maillard reaction). By decreasing the THP operating temperature from 165 degrees C to 140 degrees C, THP effluent colour decreased from 12,677 mg-PtCo L(-1) to 3837 mg-PtCo L(-1). The change in THP operating temperature from 165 degrees C to 140 degrees C was shown to have no significant impact on anaerobic biodegradability of the sludge. The rate and extent of COD biodegradation remained largely unaffected by the temperature change with an average first order hydrolysis rate of 0.19 d(-1) and conversion extent of 0.43 g-COD(CH4)g-COD(-1).

Technologies to Recover Nutrients from Waste Streams: A Critical Review

Technologies to recover nitrogen, phosphorus, and potassium from waste streams have undergone accelerated development in the past decade, predominantly due to a surge in fertilizer prices and stringent discharge limits on these nutrients. This review provides a critical state of art review of appropriate technologies which identifies research gaps, evaluates current and future potential for application of the respective technologies, and outlines paths and barriers for adoption of the nutrient recovery technologies. The different technologies can be broadly divided into the sequential categories of nutrient accumulation, followed by nutrient release, followed by nutrient extraction. Nutrient accumulation can be achieved via plants, microorganisms (algae and prokaryotic), and physicochemical mechanisms including chemical precipitation, membrane separation, sorption, and binding with magnetic particles. Nutrient release can occur by biochemical (anaerobic digestion and bioleaching) and thermochemical treatment. Nutrient extraction can occur via crystallization, gas-permeable membranes, liquid–gas stripping, and electrodialysis. These technologies were analyzed with respect to waste stream type, the product being recovered, and relative maturity. Recovery of nutrients in a concentrated form (e.g., the inorganic precipitate struvite) is seen as desirable because it would allow a wider range of options for eventual reuse with reduced pathogen risk and improved ease of transportation. Overall, there is a need to further develop technologies for nitrogen and potassium recovery and to integrate accumulation–release–extraction technologies to improve nutrient recovery efficiency. There is a need to apply, demonstrate, and prove the more recent and innovative technologies to move these beyond their current infancy. Lastly, there is a need to investigate and develop agriculture application of the recovered nutrient products. These advancements will reduce waterway and air pollution by redirecting nutrients from waste into recovered nutrient products that provides a long-term sustainable supply of nutrients and helps buffer nutrient price rises in the future. Graphical Abstract:

Anaerobic co-digestion of pig manure and algae: impact of intracellular algal products recovery on co-digestion performance.

This paper investigates anaerobic co-digestion of pig manure and algae (Scenedesmus sp.) with and without extraction of intracellular algal co-products, with views towards the development of a biorefinery concept for lipid, protein and/or biogas production. Protein and/or lipids were extracted from Scenedesmus sp. using free nitrous acid pre-treatments and solvent-based Soxhlet extraction, respectively. Processing increased algae methane yield between 29% and 37% compared to raw algae (VS basis), but reduced the amount of algae available for digestion. Co-digestion experiments showed a synergy between pig manure and raw algae that increased raw algae methane yield from 0.163 to 0.245 m(3) CH4 kg(-1)VS. No such synergy was observed when algal residues were co-digested with pig manure. Finally, experimental results were used to develop a high-level concept for an integrated biorefinery processing pig manure and onsite cultivated algae, evaluating methane production and co-product recovery per mass of pig manure entering the refinery.

Removal of sulfate from high-strength wastewater by crystallisation

Sulfate causes considerable problems in anaerobic digesters, related to generation of sulfides, loss of electrons (and hence methane), and contamination of gas streams. Removal of sulfides is generally expensive, and still results in methane losses. In this paper, we evaluate the use of precipitation for low-cost sulfate removal, in highly contaminated streams (>1 gS L(-1)). The main precipitate assessed is calcium sulfate (gypsum), though the formation of complex precipitates such as jarosite and ettringite to remove residual sulfate is also evaluated. The four main concerns in contaminated wastewater are:- high solubility, caused by high ion activity and ion pairing; slow kinetics; inhibition of nucleation; and poisoning of crystals by impurities, rendering product unsuitable for reuse as seed. These concerns were addressed through batch experiments on a landfill wastewater with a similar composition to other sulfate rich industrial wastewaters (high levels of organic and inorganic contaminants). Crystallisation rates were rapid and comparable to what is observed by others for pure solutions (2-5 h). The kinetics of crystallisation showed a 2nd order dependence on supersaturation, which have implications for crystalliser design, as discussed in the paper. No spontaneous nucleation was observed (seed was required). Seed poisoning did not occur, and product crystals were as effective as pure seed. Solubility was increased by an order of magnitude compared to a pure solution (2.6x10(-3) M2 vs. 0.22x10(-3) M2). As evaluated using equilibrium modelling, this was caused equally by non-specific ion activity, and specific ion pairing. Jarosite and ettringite could not be formed at reasonable pH and temperature levels. Given the lack of complex precipitates, and relatively high solubility, gypsum crystallisation cannot practically be used to remove sulfate to very low levels, and gas-sulfide treatment will likely still be required. It can however, be used for low-cost bulk removal of sulfate.

Removal of Persistent Organic Contaminants by Electrochemically Activated Sulfate.

Solutions of sulfate have often been used as background electrolytes in the electrochemical degradation of contaminants and have been generally considered inert even when high-oxidation-power anodes such as boron-doped diamond (BDD) were employed. This study examines the role of sulfate by comparing electro-oxidation rates for seven persistent organic contaminants at BDD anodes in sulfate and inert nitrate anolytes. Sulfate yielded electro-oxidation rates 10-15 times higher for all target contaminants compared to the rates of nitrate anolyte. This electrochemical activation of sulfate was also observed at concentrations as low as 1.6 mM, which is relevant for many wastewaters. Electrolysis of diatrizoate in the presence of specific radical quenchers (tert-butanol and methanol) had a similar effect on electro-oxidation rates, illustrating a possible role of the hydroxyl radical ((•)OH) in the anodic formation of sulfate radical (SO4(•-)) species. The addition of 0.55 mM persulfate increased the electro-oxidation rate of diatrizoate in nitrate from 0.94 to 9.97 h(-1), suggesting a nonradical activation of persulfate. Overall findings indicate the formation of strong sulfate-derived oxidant species at BDD anodes when polarized at high potentials. This may have positive implications in the electro-oxidation of wastewaters containing sulfate. For example, the energy required for the 10-fold removal of diatrizoate was decreased from 45.6 to 2.44 kWh m(-3) by switching from nitrate to sulfate anolyte.

Anaerobic digestion of spent bedding from deep litter piggery housing

This paper investigates spent litter from deep litter piggery housing as a potential substrate for farm-scale anaerobic digestion. Degradability and degradation rates were evaluated under mesophilic conditions for unused, lightly soiled (used by weaner/small pigs), and heavily soiled (used by finishing/large pigs) wheat straw, barley straw, and rice husks bedding. Apparent first order hydrolysis rate coefficients varied, but were comparable across all samples analysed (<0.1 day(-1)). Spent wheat straw was generally more degradable (approximately 60%) than spent barley straw, while spent barley straw was comparable to raw straw (40-50%), but with higher hydrolysis rates, indicating better accessibility. Rice husks were relatively poorly degradable (<20%), but degradability was improved by weathering in a pig shed. Digestion of spent barley and wheat straw litter was significantly faster (approximately twice the rate) at low (8% solids) than high (14% solids) solids loading. Rice husks degradation kinetics were not significantly influenced by solids concentration. Intrinsic methanogenic activity of heavily soiled spent wheat straw and rice husks bedding was initially poor, but achieved full activity after 40-60 days, indicating that reactor operation without external inoculum may be possible with care.

Breakage and growth towards a stable aerobic granule size during the treatment of wastewater

To better understand granule growth and breakage processes in aerobic granular sludge systems, the particle size of aerobic granules was tracked over 50 days of wastewater treatment within four sequencing batch reactors fed with abattoir wastewater. These experiments tested a novel hypothesis stating that granules equilibrate to a certain stable granule size (the critical size) which is determined by the influence of process conditions on the relative rates of granule growth and granule breakage or attrition. For granules that are larger than the critical size, granule breakage and attrition outweighs granule growth, and causes an overall reduction in granule size. For granules at the critical size, the overall growth and size reduction processes are balanced, and granule size is stable. For granules that are smaller than the critical size, granule growth outweighs granule breakage and attrition, and causes an overall increase in granule size. The experimental reactors were seeded with mature granules that were either small, medium, or large sized, these having respective median granule sizes of 425 μm, 900 μm and 1125 μm. An additional reactor was seeded with a mixture of the sized granules to represent the original source of the granular sludge. The experimental results were analysed together with results of a previous granule formation study that used mixed seeding of granules and floccular sludge. The analysis supported the critical size hypothesis and showed that granules in the reactors did equilibrate towards a common critical size of around 600-800 μm. Accordingly, it is expected that aerobic granular reactors at steady-state operation are likely to have granule size distributions around a characteristic critical size. Additionally, the results support that maintaining a quantity of granules above a particular size is important for granule formation during start-up and for process stability of aerobic granule systems. Hence, biomass washout needs to be carefully managed to optimize granule formation during the reactor start-up.

A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in wastewater treatment process models.

There is a growing interest within the Wastewater Treatment Plant (WWTP) modelling community to correctly describe physico-chemical processes after many years of mainly focusing on biokinetics. Indeed, future modelling needs, such as a plant-wide phosphorus (P) description, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems. In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation/pairing is presented and interfaced with industry standard models. The module accounts for extensive consideration of non-ideality, including ion activities instead of molar concentrations and complex ion pairing. The general equilibria are formulated as a set of Differential Algebraic Equations (DAEs) instead of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies. The latter is reinforced with the Simulated Annealing method to increase the robustness of the solver making the system not so dependent of the initial conditions. Simulation results show pH predictions when describing Biological Nutrient Removal (BNR) by the activated sludge models (ASM) 1, 2d and 3 comparing the performance of a nitrogen removal (WWTP1) and a combined nitrogen and phosphorus removal (WWTP2) treatment plant configuration under different anaerobic/anoxic/aerobic conditions. The same framework is implemented in the Benchmark Simulation Model No. 2 (BSM2) version of the Anaerobic Digestion Model No. 1 (ADM1) (WWTP3) as well, predicting pH values at different cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated, by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling studies can be complemented with a rigorous description of aqueous phase and ion chemistry (pH, speciation, complexation).

Modelling phosphorus (P), sulfur (S) and iron (Fe) interactions for dynamic simulations of anaerobic digestion processes.

This paper proposes a series of extensions to functionally upgrade the IWA Anaerobic Digestion Model No. 1 (ADM1) to allow for plant-wide phosphorus (P) simulation. The close interplay between the P, sulfur (S) and iron (Fe) cycles requires a substantial (and unavoidable) increase in model complexity due to the involved three-phase physico-chemical and biological transformations. The ADM1 version, implemented in the plant-wide context provided by the Benchmark Simulation Model No. 2 (BSM2), is used as the basic platform (A0). Three different model extensions (A1, A2, A3) are implemented, simulated and evaluated. The first extension (A1) considers P transformations by accounting for the kinetic decay of polyphosphates (XPP) and potential uptake of volatile fatty acids (VFA) to produce polyhydroxyalkanoates (XPHA) by phosphorus accumulating organisms (XPAO). Two variant extensions (A2,1/A2,2) describe biological production of sulfides (SIS) by means of sulfate reducing bacteria (XSRB) utilising hydrogen only (autolithotrophically) or hydrogen plus organic acids (heterorganotrophically) as electron sources, respectively. These two approaches also consider a potential hydrogen sulfide ( [Formula: see text] inhibition effect and stripping to the gas phase ( [Formula: see text] ). The third extension (A3) accounts for chemical iron (III) ( [Formula: see text] ) reduction to iron (II) ( [Formula: see text] ) using hydrogen ( [Formula: see text] ) and sulfides (SIS) as electron donors. A set of pre/post interfaces between the Activated Sludge Model No. 2d (ASM2d) and ADM1 are furthermore proposed in order to allow for plant-wide (model-based) analysis and study of the interactions between the water and sludge lines. Simulation (A1 - A3) results show that the ratio between soluble/particulate P compounds strongly depends on the pH and cationic load, which determines the capacity to form (or not) precipitation products. Implementations A1 and A2,1/A2,2 lead to a reduction in the predicted methane/biogas production (and potential energy recovery) compared to reference ADM1 predictions (A0). This reduction is attributed to two factors: (1) loss of electron equivalents due to sulfate [Formula: see text] reduction by XSRB and storage of XPHA by XPAO; and, (2) decrease of acetoclastic and hydrogenotrophic methanogenesis due to [Formula: see text] inhibition. Model A3 shows the potential for iron to remove free SIS (and consequently inhibition) and instead promote iron sulfide (XFeS) precipitation. It also reduces the quantities of struvite ( [Formula: see text] ) and calcium phosphate ( [Formula: see text] ) that are formed due to its higher affinity for phosphate anions. This study provides a detailed analysis of the different model assumptions, the effect that operational/design conditions have on the model predictions and the practical implications of the proposed model extensions in view of plant-wide modelling/development of resource recovery strategies.