Fermoso UASB

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Metal supplementation to UASB bioreactors: from cell-metal interactions to full-scale application

Fernando G. Fermosoa , Jan Bartaceka,b , Stefan Jansenc,1 , Piet N.L. Lensa,b,
a Sub-department of Environmental Technology, Wageningen University, Biotechnion-Bomenweg 2, P.O. Box 8129, 6700 EV Wageningen, The Netherlands b Pollution Prevention and Control core, UNESCO-IHE, P.O. Box 3015, 2601 DA Delft, The Netherlands c Laboratory of Physical Chemistry and Colloid Science, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands
AR TIC LE D ATA
Article history: Received 29 May 2008 Received in revised form 16 October 2008 Accepted 16 October 2008 Available online 16 December 2008 Keywords: Metal supplementation UASB Granular sludge Metal requirements
ABSTR ACT
Upflow anaerobic sludge bed (UASB) bioreactors are commonly used for anaerobic wastewater treatment. Trace metals need to be dosed to these bioreactors to maintain microbial metabolism and growth. The dosing needs to balance the supply of a minimum amount of micronutrients to support a desired microbial activity or growth rate with a maximum level of micronutrient supply above which the trace metals become inhibitory or toxic. In studies on granular sludge reactors, the required micronutrients are undefined and different metal formulations with differences in composition, concentration and species are used. Moreover, an appropriate quantification of the required nutrient dosing and suitable ranges during the entire operational period has been given little attention. This review summarizes the state-of-the-art knowledge of the interactions between trace metals and cells growing in anaerobic granules, which is the main type of biomass retention in anaerobic wastewater treatment reactors. The impact of trace metal limitation as well as overdosing (toxicity) on the biomass is overviewed and the consequences for reactor performance are detailed. Special attention is given to the influence of metal speciation in the liquid and solid phase on bioavailability. The currently used methods for trace metal dosing into wastewater treatment reactors are overviewed and ways of optimization are suggested. 2008 Elsevier B.V. All rights reserved.
1.
Introduction
Most industrial effluents contain trace quantities of a variety of metals, of which many are classified as priority pollutants (EC, 2000). Microbial biofilms, natural or engineered, can be used to remediate heavy metal pollution by biochemical modification and/or the accumulation of toxic metal ions (Muoz et al., 2006; Singh et al., 2006). An understanding of the fate of metals in biofilms, as anaerobic granular sludge, is
crucial for the successful design of biological wastewater treatment systems that are used for biodegrading organic contaminants, which are frequently intermingled with metal pollution (Singh et al., 2006). Most of these metals are also necessary for biological growth or activity, and absence of sufficient quantities limits the activity of the microbial population present in the anaerobic bioreactors (Fermoso et al., 2008c). As technological changes take place in the manufacturing or industrial process,
Corresponding author. Sub-department of Environmental Technology, Wageningen University, Biotechnion-Bomenweg 2, P.O. Box 8129, 6700 EV Wageningen, The Netherlands. E-mail address: Piet.Lens@wur.nl (P.N.L. Lens). 1 Present address: TNO/Deltares, Soil and Subsurface Systems, Princetonlaan 6, PO Box 85467, 3508 AL Utrecht, The Netherlands. 0048-9697/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.scitotenv.2008.10.043
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the compounds discharged and thus also the wastewater characteristics change (Pons et al., 2004). The exact amounts of trace nutrients needed varies for the different types of wastewaters (Anon, 2000; Liang et al., 2007). Nowadays, trial approaches are used to asses their benefit for anaerobic processes (Opure BV, personal communication). The metal dosing can be optimized by a better fundamental insight in the
chemical, microbiological and engineering aspects determining the metal requirements of UASB reactors. The Upflow Anaerobic Sludge Bed (UASB) process is the most applied process for the anaerobic treatment of industrial effluents (Van Lier, 2008). In this process, granular sludge, a spherical biofilm developed by autoaggregation of cells (Lettinga et al., 1979), is formed (Fig. 1A). The aim of
Fig. 1 (A) Multidisciplinary approach and (B) analytical infrastructure required for determining the interactions of metals with the solid phase, liquid phase and the microorganisms present in anaerobic bioreactors, which leads to a more rational and efficient metal supply to bioreactors. UASB reactor: Upflow anaerobic sludge bed reactor; AVS: Acid volatile sulfide; DMT: Donnan membrane technique; SMA: Specific methanogenic activity.
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Table 1 Role of some essential trace elements in various enzymes involved in anaerobic reactions and transformation. Element
Cu
2.
2.1.
Metalsmicrobe interaction
Role of metals in the enzymatic system
Functions
Superoxide dismutase Hydrogenase (Facultative anaerobes) Nitrite reductase Acetyl-CoA synthase B12-enzymes COdehydrogenase Methyltransferase Hydrogenase COdehydrogenase Methane monooxygenase NO-reductase Superoxide dismutase Nitrite and Nitrate reductase Nitrogenase Stabilize methyltransferase in methaneproducing bacteria. Redox reactions Formate dehydrogenase Nitrate reductase Nitrogenase
Element
Ni
Functions
CO-dehydrogenase Acetyl-CoA synthase Methyl-CoM reductase (F430) Urease Stabilize DNA, RNA Hydrogenase Hydrogenase Formate dehydrogenase Glycin reductase Formate dehydrogenase Formylmethanofurandehydrogenase Aldehydeoxydoreductase Antagonist of Mo
Co
Se
Fe
Mn
Zn
Hydrogenase Formate dehydrogenase Superoxide dismutase
Mo
Nitrogenase Chloroperoxydase Bromineperoxydase
Metals are important in all biochemical processes in any kind of living organism. Of the 95 naturally occurring elements of the periodic table, no less than 25 have an essential biological function (Frnzle and Markert, 2002). Some of these, e.g. zinc, nickel, copper, selenium, cobalt, chromium, molybdenum, tungsten, manganese or iodine are required in small amounts and are termed essential trace elements. Most of them are part of the active site of enzymes. Table 1 lists the role of some essential trace elements in various enzymes catalyzing anaerobic reactions and transformations (Oleszkiewicz and Sharma, 1990; Zandvoort et al., 2006b). The presence of high metal concentrations in a bulk liquid does not mean that microorganisms take the metal up and incorporate it into the catalytic centers of their enzymes (Ermler, 2005). For instance, microorganisms take up metals also in the form of complexes, such as e.g. Vitamin B12 (Ferguson and Deisenhofer, 2004), Co-citrate (Krom, 2002) or bound to siderophores (Worms et al., 2006). More in general, in between the presence of metals in the bulk liquid and the actual biological effects, complex processes as biouptake and biosynthesis play an important role. Some of these processes are discussed in more detail later in this review. Heavy metals act as inhibitors by blocking enzyme functions. The toxic effect of heavy metals is primarily nonspecific and reversible (Nies, 1999). This type of inhibition is characterized by the reversible binding of the inhibitor with either the enzyme or the enzyme-substrate complex. Less frequently, metals act as competitive inhibitors (they compete with the substrate). This type of inhibition depends on the affinity of the metal and enzyme, as well as on the relative concentrations of the competing metals (Oleszkiewicz and Sharma, 1990).
this review is to summarize the knowledge required to understand the metal nutrient requirements and facilitate design of metal supplementation in UASB reactors (Fig. 1). The description of the interactions between metals and microbes are given first. This allows to understand the role that metals have in microbial systems, e.g. the role of metals in enzymatic functioning and concepts of metal uptake. The next step to gain a deeper knowledge of the trace metal requirements in UASB reactors is the study of the possible interactions between trace metals and UASB granules. The role of metal speciation in the reactor liquid media is evaluated as well. Metal precipitation, dissolution and complexation with organic and inorganic ligands play an important role in the fate of metals in UASB reactors. The metal requirements of UASB reactors are then assessed by describing the impact of trace metal limitation on the microbial activity on the one hand and the toxic effects caused by an excess of them on the other hand. Subsequently, different trace metal dosing strategies are reviewed and evaluated. Finally, recommendations for future research in the field of trace metal supplementation are given.
2.2.
Metal uptake into the cell
It is generally accepted that the speciation of metals has a huge impact on their uptake (and ensuing biological effects), as has been demonstrated in detail for algae and some microorganisms (Hudson, 1998; Slaveykova et al., 2004; Sunda and Huntsman, 1998). In general, the transport of metal ions is to a great extent determined by the properties of the transport systems (Braun et al., 1998). For instance, transport of cobalt and nickel is reported to proceed either via specific cobalt and/or nickel transporters, or via magnesium transporters, e.g. for cobalt (Degen et al., 1999; Kobayashi and Shimizu, 1999; Komeda et al., 1997; Pogorelova et al., 1996; Saito et al., 2002); and nickel (Eitinger and Mandrand-Berthelot, 2000; Mulrooney and Hausinger, 2003; Watt and Ludden, 1999). The uptake of metal ions by these specific transporters can be described by Michaelis Menten kinetics, where the bioavailable metal ion is first bound by a transporter site and subsequently taken up. The binding properties determine the affinity of the transporter to the metal, while the amount of the transporter determines the maximum uptake rate. Both of these parameters can change
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have been reported to be taken up as well (Phinney and Bruland, 1994). Furthermore, biological responses can have a significant impact on the metal speciation and bioavailability in the exposure media due to excretion and changes of the uptake properties (Slaveykova et al., 2004). These toxicity models were established and verified for natural waters and higher organisms such as freshwater algae Chlorella kesslerii (Hassler et al., 2004), Urchin larvae (Lorenzo et al., 2006) or mussels (Mytilus galloprovincialis) (Beiras et al., 2003). Thus far, this type of models has never been applied to the anaerobic consortia present in biofilms or granules from wastewater treatment reactors.
Fig. 2 Conceptual framework of the FIAM and BLM, including (1) mass transport of the free metal (Mz+) and a hydrophilic complex (ML) in solution; (2) dissociation/complexation with a ligand in solution; (3) specific (M-Rcell) or non-specific (M-Acell) adsorption of the metal to the surface of the organism; (4) metal transport into the organism characterized by an internalization rate constant (kint) and a subsequent reaction an intracellular ligand (MLbio); (5) expression of the biological effect. The box identifies the reactions that are taken into account in the FIAM and BLM (After Hassler et al., 2004).
3.
3.1.
Metalsbiofilm interaction
Metal bioavailability in granular sludge
with changing chemistry or biology. Different metal ions can compete for the same uptake site, thus affecting the conditional affinity (Sunda and Huntsman, 1998). Furthermore, the organism can actively decrease or increase the number of transporters in response to its environment (Worms et al., 2006), thus affecting the maximum uptake rates. To quantify metal toxicity on biological systems, Pagenkopf (1983) proposed the Gill Surface Interaction Model (GSIM), while Morel (1983) formulated the Free-Ion Activity Model (FIAM), schematically demonstrated in Fig. 2. Both the GSIM and FIAM are the theoretical predecessors of the Biotic Ligand Model (BLM) (Niyogi, 2004).The BLM has been proposed as a tool to evaluate quantitatively the manner in which water chemistry affects the speciation and biological availability of metals in aquatic organisms, such as fish or Daphia magna (Niyogi, 2004). This is an important consideration because it is the bioavailability and bioreactivity of metals that control their potential to cause adverse effects (Paquin et al., 2002). The BLM is based on the hypothesis that toxicity is not simply related to the total aqueous metal concentration, but that both metalligand complexation and metal interactions with competing cations at the site of toxic action need to be considered (Meyer et al., 1999; Pagenkopf, 1983). The BLM model relies on the assumption that the processes outside the organism are at equilibrium. This simple model has been criticized, since its applicability has been shown to be limited (Campbell et al., 2002; Hassler et al., 2004). For instance, diffusion limitation, as expected to occur at low concentrations, in combination with high affinity uptake sites, will certainly cause deviations (Hudson, 1998). In these cases, labile species will also be bioavailable (Van Leeuwen, 1999). Secondly, not only free metal ions, but also lipophilic complexes, and sometimes even hydrophilic complexes,
Metal sorption by anaerobic granules and similar aggregates has been studied by many authors (Artola et al., 2000; Gonzalez-Gil et al., 2001; Gould and Genetelli, 1978; MacNicol and Beckett, 1989; Osuna et al., 2003; Zandvoort et al., 2004). Overall, these studies confirm strong sorption of metal ions in granules due to precipitation, coprecipitation, adsorption and binding by Extracellular Polymeric Substance (EPS) and bacterial cells. EPS are major components of granular matrix, and up to 90% of the dry biomass is EPS material (Gao et al., 2008), which bind metals (Guibaud et al., 2008). Furthermore, the bacterial interface itself can also serve as an important metal binding surface (Aksu et al., 1991). X-ray analysis of UASB granules has confirmed the existence of copper, iron, zinc and nickel sulfide precipitates (Fang and Liu, 1995; Gonzalez-Gil et al., 2001; Kaksonen et al., 2003; Liu and Fang, 1998). The bioavailability and mobility of essential trace metals in the UASB reactors are mainly controlled by the sulfide chemistry (Van der Veen et al., 2007). On the basis of stability constants from literature (Martell & Smith, 1989) and the composition of the anaerobic wastewater environments, metal ions are expected to precipitate with sulfide, carbonate and phosphate in the pore water present in the granular matrix. Metal sulfide precipitation is expected to be the most important process. The predominating role of sulfides in metal fixation in anaerobic granules is supported by the high acid volatile sulfide (AVS) content and the high metal content in the oxidizable (containing both sulfidic and organic bonding forms) fraction present in UASB systems (Van der Veen et al., 2007). As metal sulfides have a very low solubility product (Martell and Smith, 1989), it would be expected that these metals are non-bioavailable to the methanogenic consortia. Jansen et al. (2007) proposed nevertheless that in most cases, the dissolution rates of cobalt and nickel sulfides do not limit the methanogenic activity in anaerobic wastewater treatment. It should, however, be noted that this was based on batch experiments with methanogenic enrichments and freshly prepared metal sulfide precipitates. Ageing of sulfidic precipitates, which takes place in the sludge during reactor operation, will lower the dissolution rates and might therefore lower the metal bioavailability (Gonzalez-Gil et al., 2003).
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The bioavailability of retained metals in granular sludge can be assessed from the bonding form distribution, although the fractions are operationally-defined and not phase-specific (Van Hullebusch et al., 2005). The fractions possess a decreasing solubility/reactivity from the first to the last step. This decreasing solubility can be used as a measure of potential bioavailability (Jong and Parry, 2004), beginning with the exchangeable fraction, the most bioavailable, the carbonate fraction, the organic matter/sulfide fraction and the last fraction, residual, the least bioavailable.
3.2.
Metal toxicity in granular sludge
There is only a small difference between the optimal and toxic free cobalt concentration: the optimal concentration is approximately 7 mol L 1 with an apparent KM value of 0.9 mol L 1 (based on total cobalt addition) (Zandvoort et al., 2002a), whereas a free cobalt concentration of only around 18 mol L 1 is already significantly (50% inhibition) toxic (Bartacek et al., 2008). This means that in case only a small amount of complexing agents is present in the medium, a relatively low total cobalt concentration will cause operational problems with anaerobic reactors. Metal toxicity cannot be evaluated solely based on the metal precipitated/sorbed in methanogenic granular sludge, but requires also the determination of the speciation of metals present in the bulk solution (Paquin et al., 2000; Plette et al., 1999; Shuttleworth and Unz, 1991). Although not only the free cobalt species can be transported into a microbial cell, Bartacek et al. (2008) suggested that toxicity of cobalt can be assessed based on the free cobalt concentration. The latter statement is only valid when the process conditions such as pH and concentration of competing metals (namely calcium or magnesium) are kept constant. The donnan membrane technique (DMT) was successfully used for measurement of the free cobalt (Co2+) concentration in anaerobic granular sludge (Bartacek et al., 2008). Similarly, Temminghoff et al. (2000) obtained a good agreement between calculated and measured (with the DMT) free metal concentrations for copper and cadmium with and without inorganic or (synthetic as well as natural) organic complexation. A practical problem of the DMT setup as used by Bartacek et al. (2008) is the long time required to obtain experimental data (4 days for equilibrium establishment, five days for DMT measurement). This disables DMT for measurements of free metal concentrations under dynamic conditions in bioreactors.
structure of the metal sulfide precipitate should be known. Secondly, the errors in the literature values for the solubility products are very large, and different literature sources give different values. Thirdly, precipitation equilibrium is actually not reached in many cases due to kinetic limitations. And finally, size and ligand effects can affect precipitation. Apart from precipitation in the form of well defined precipitates, coprecipitation and adsorption are also important phenomena in a mixture of metal ions. These processes have been studied in sediments, typically containing excess of iron over other metals (Cooper and Morse, 1999; Huerta-Diaz et al., 1998; Morse and Luther, 1999). Considerable adsorption and coprecipitation of cobalt and nickel on FeS (mackinawite) occurs (Morse and Arakaki, 1993). Kinetic factors can further influence coprecipitation (Morse and Luther, 1999).
4.2.
Liquid phase speciation
4.
4.1.
Metalsliquid phase interaction

Particulate metal binding
As for the pore water in the granular biofilm, metal sulfide precipitation is expected to be the most important process in metal precipitation in the anaerobic media present in the UASB reactor: the low solubility product of metal sulfides will result in extremely low free metal ion concentrations (Martell and Smith, 1989). However, one has to be careful in trying to predict free metal ion concentrations from these solubility products. In the first place, to know the solubility product, the crystal
Sulfide is not only important because of the formation of metal precipitates, but also because of the formation of dissolved metal complexes. Dissolved metal sulfide species have only been studied over the last 20 years, and theoretical estimates date back only some 20 years (Dyrssen, 1988), while measurements are available only since 15 years (Al-Farawati and Van Den Berg, 1999; Luther et al., 1996; Zhang and Millero, 1994). Although the data vary, they demonstrate that dissolved metal sulfide complexes are very strong. Other important inorganic ligands are CO2 and PO3. 3 4 Although the complexes are less strong than the metal sulfide complexes, the importance of carbonate and phosphate complexes was demonstrated for anaerobic media (Bartacek et al., 2008; Callander and Barford, 1983). Carbonate is very important because of its high concentration in wastewaters, and its strong binding with metal ions, especially with Ni(II). Unfortunately, some disagreement about the binding constant exists in the literature (Hummel and Curti, 2003; Turner et al., 1981). The ligands OH, SO2 and Cl are also present at large 4 concentrations, but are relatively unimportant because of their weak binding. Metal binding by Soluble Microbial Products (SMPs) was demonstrated for nickel (Kuo and Parkin, 1996; Kuo et al., 1996) and copper (Bender et al., 1970). Strong zinc complexing ligands were detected by voltammetry in media after growth of sulfate reducing bacteria (Bridge et al., 1999). The results suggest that excretion of metal binding SMP can serve as a mechanism to reduce metal toxicity. It is still an open question whether the microorganisms in anaerobic wastewater treatment systems actively excrete organic metal ligands to bind metals in order to overcome limitation, as is known for iron (Neilands, 1995) and cobalt (Saito et al., 2002). Apart from organic ligands produced by microorganisms, sometimes organic ligands are added. First, some organic substrates can have metal binding properties, e.g. in the case of acetate. However, most of these complexes are weak compared to the strong complexes with sulfide (Martell and Smith, 1989). Furthermore, sometimes synthetic ligands such as EDTA, NTA or citrate are added. In some cases they are added deliberately, for instance to keep the metals dissolved (Bretler and Marison, 1996; Hartung, 1992), in other cases they are present in the waste stream, possibly as waste products (Nowack, 2002).
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Organic ligands might influence precipitation. In general, in their presence, the concentration of dissolved metal is increased. However, conflicting data are also found. For instance, in a system containing Ag+ and amorphous FeS, dissolved Ag+ was smaller than predicted in the presence of high concentrations of the thiol compounds 3-mercaptopropanoic acid and cysteine (Adams and Kramer, 1998). A possible explanation for this could be the binding of the Agthiol complexes to FeS (Adams and Kramer, 1998). In another study, the solubility of CuS was increased by thiols, while that of PbS and CdS was not (Shea and MacCrehan, 1988a,b). Furthermore, organic ligands can affect the size (Pommerenk and Schafran, 2005) and kinetics (see below) of precipitation.
4.3.
Kinetics of precipitation and complex formation
Within the dynamic bioreactor environment, relative rates of the various processes can be of great importance, in particular the kinetics of particulate formation and dissolution. Precipitation can be divided into 5 stages (Nielsen, 1964): nucleation, growth of nuclei, aggregation, formation of irreversible aggregates and formation of larger crystals at the
expense of smaller ones. In parallel with step 5, precipitates age, generally transforming from amorphous precipitates to more stable crystalline forms. Metal sulfide dissolution in near neutral pH ranges has only been studied for mackinawite (FeS) (Pankow and Morgan, 1979, 1980) and for similar systems such as sediments (Harper et al., 1998; Motelica-Heino et al., 2003). Besides precipitation, the kinetics of adsorption onto and desorption from precipitates can be very important, as exemplified by the coprecipitation/adsorption kinetics of copper, zinc, lead and cadmium to FeS (Davis et al., 1994). The kinetics of precipitation and dissolution are influenced by organic ligands: they can decrease the precipitation rate (Helz and Horzempa, 1983; Shea and Helz, 1987) or increase the dissolution rate, e.g. in case of siderophores (Cervini-Silva and Sposito, 2002; Kraemer and Hering, 1997; Liang et al., 2000). Besides the reaction kinetics involving the particulate matrix, the rates of processes within the dissolved metal fraction can be important. In aqueous solutions, the rate of metal complex formation largely depends on the water loss rate constants of the metal ions (Morel, 1983), independent of the nature of the ligand. From this so called Eigen mechanism, the order of the reaction rates of some of the relevant metal ions is given as: Fe2+ N Co2+ N Ni2+. Especially for Ni2+, complexation reactions are known to be relatively slow (Margerum et al., 1978).
Fig. 3 (A) Boundary conditions for metal addition to keep the UASB reactor efficiency optimal. (B) Effect of cobalt concentration on methanogenic activity using methanol as substrate (pH 7.0; 30 C) of anaerobic granular sludge present in the UASB reactors. () 5 M cobalt (optimal), () 0 M cobalt (limitation) and () 100 M cobalt (toxicity).
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Furthermore, in solutions containing high concentrations of competing ions such as Ca2+ and Mg2+, exchange reactions can be inherently slow (Hering and Morel, 1989, 1990).
understood (Zandvoort et al., 2006b). Thus, knowledge about the effect of metals in the biomass and the metal distribution through the UASB system is necessary in order to obtain a proper strategy for metal supplementation.
5.
MetalsUASB interaction
5.1. 5.1.1.
Metal limitation in UASB reactors Methanol fed bioreactors
Metal supplementation in UASB reactors is a compromise between achieving the maximal biological activity of the biomass present in the reactor, while minimizing the costs of the supplied metal and the metal losses into the environment. The boundary conditions to keep a stable reactor operation vary between nutrient deficiency due to lack of essential metals and toxicity due to their excess (Fig. 3). The metal addition strategy affects the metal losses and costs of the added metal in order to achieve the optimal metal concentration inside the UASB reactor. In literature, different metal formulations have been used in studies on UASB reactors, but they differ in composition, concentration and the forms in which they are supplemented to the feed (Singh et al., 1999; Tiwari et al., 2006; Zandvoort et al., 2004). Also, the appropriate quantification and suitable ranges in which nutrient dosing is required during the entire operational period are poorly
Omission of a divalent cation metal (cobalt, nickel or zinc) from the feed of methanol-fed anaerobic granular sludge bioreactors leads to a reduced specific methanogenic activity (SMA) on methanol and, consequently, to methanol accumulation in the effluent, followed by the enhanced formation of acetate as shown in Fig. 4 (Fermoso et al., 2008b,c,d). Thus, during methylothrophic methanogenic degradation of methanol, the decrease of SMA of the sludge with methanol as the substrate is the variable to follow for predicting possible methanol accumulation, further acetate accumulation and ultimately complete reactor acidification. The time period required to achieve nickel limitation (140 days of operation, (Fermoso et al., 2008d)), as also observed by Zandvoort et al. (2002b), was much longer compared to that required for cobalt limitation, which is already achieved in
Fig. 4 (A) Proposed outline of the mechanism of induction of metal limitation in methanol-fed UASB reactors. Numbers indicate predominant process. (1) methylotropihic methanogenesis. (2) acetogenesis. (3) acetotrophic methanogenesis. SMA: specific methanogenic activity with methanol as the substrate (After Fermoso et al., 2008a,b,c). (B) Decay of SMA with methanol as the substrate over time due to absence of cobalt addition in the feed of a methanol-fed UASB reactor (pH 7.0; 30 C; Organic loading rate: 10 g COD L 1 d 1). Day 0 indicates the pulse addition of cobalt (5 M, cobalt in vitamin B12) to the bioreactor; days 15 to 0 clearly illustrate a trace metal (cobalt) limited reactor operation.
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15 days (Fermoso et al., 2008c). Kida et al. (2001) observed that the methanogenic activity with acetate as the substrate (pH 7, 37 C), as well as the F430 and corrinoid concentrations in methanogenic mesophilic biomass from a sewage treatment plant decreased with decreasing amounts of Ni2+ and Co2+ supplied. The omission of nickel might thus result in a reduced amount of coenzyme F430, thereby decreasing the SMA of the sludge. The reduced SMA in the absence of nickel was not observed until day 129 (Fermoso et al., 2008d). The initial concentration of nickel in the seed sludge (43 g g TSS 1) was probably enough to support the enzymatic activity and synthesis of coenzyme F430 for a considerably long time, even if the size of the Methanosarcina population increased. Moreover, many organisms respond to a lower metal bioavailability by an increased synthesis of metal transporters (Sunda and Huntsman, 1998). This type of adaptation to low nickel concentrations might also have contributed to the longer time-period before a decrease in methylotrophic activity is observed (Zandvoort et al., 2002b). Only a few papers have addressed deprivation of other essential metals during methanogenesis, as zinc or iron. Osuna et al. (2002) studied metal deprivation in VFA fed UASB reactors. The latter authors found that when adding solely zinc to the medium, the SMA with acetate as the substrate of metal deprived sludge increased by 36%. Sauer and Thauer (1997) found in enzymatic studies that the transfer of the methyl group from CH3-MT1 to coenzyme M by MT2 involved in methanol degradation depends on the Zn2+ concentration. The K M value of this transfer reaction amounted to 0.25 nM free Zn2+. This KM value is around 240 times lower than the dissolved zinc concentration in the synthetic wastewater of a zinc limited methanol fed UASB reactor (60 nM) at the moment zinc limitation has developed (Fermoso et al., 2008b). The metalbiofilm interactions induce differences between the Km value found by Sauer and Thauer (1997) (with enzymes) and the dissolved zinc concentration at the time of zinc limitation found by Fermoso et al. (2008b) (with sludge granules). Cobalt, nickel and zinc are components of different enzymes involved in anaerobic methanol degradation (Fermoso et al., 2008b,c,d). This suggests that also other metals present in the enzyme system involved in methanol degradation may follow the same pattern as well, e.g. iron which is present in heterodisulfide reductase (Deppenmeier et al., 1999) or copper which is present in Acetyl-CoA synthase (Seravalli et al., 2003).
Propionate is a key intermediate in the conversion of complex organic matter under methanogenic conditions (De Bok et al., 2004). Propionate oxidation can only proceed if the product H2 and formate are removed by methanogens or other H2 or formate utilizing bacteria (Stams, 1994). Molybdenum, tungsten and selenium are essential trace metals and are often essential for enzymes catalyzing reactions, such as formate dehydrogenase (FDH), which catalyze formate production by propionate oxidizers (Dong et al., 1994). In defined cocultures of Syntrophobacter fumaroxidans and Methanospirillum hungatei, grown on propionate, molybdenum and tungsten limitation lowered the methane production rate and the FDH activity in cell extracts of each organism (Jiang, 2006). Therefore, in case of insufficient amounts of molybdenum and tungsten are present in the influent, a limitation of propionate oxidation is likely to develop in full scale reactors with propionate as a key-intermediate.
5.2.
Metal toxicity in bioreactors
Trace metals at a too high concentration can cause inhibition of the methanogenic process (Bhattacharya et al., 1995; Ram et al., 2000). Although heavy metal toxicity in UASB reactors has been studied abundantly, reported values of toxic concentrations vary considerably between different authors (Fang, 1997; Fang and Hui, 1994; Karri et al., 2006; Lin and Chen, 1997, 1999). In view of the importance of nickel and cobalt in methanogenic processes, toxicity studies of these metals are of high importance. The inhibition of methanogenic activity from anaerobic sludge by nickel and cobalt has been studied abundantly and high differences in toxic concentrations were found (Table 2). This is due to the fact that most authors report the total metal concentration in the liquid phase, and do not consider metal speciation. Therefore, the observed toxic concentrations are affected by differences in medium composition, which causes changes in metal speciation (Jansen et al., 2007; Worms et al., 2006).
5.3. 5.3.1.
Metal dosing Metal dosing requirements
5.1.2.
Other substrates in anaerobic bioreactors
Zandvoort et al. (2006a) screened four full-scale bioreactors for their response to trace metals, using three methanogenic substrates, viz. methanol, acetate and H2/CO2. The four reactors treat alcohol distillery wastewater, paper mill wastewater, groundwater contaminated with perchloroethane and brewery wastewater. In accordance with Section 5.1.1., Zandvoort et al. (2006b) observed a significant response using methanol as the substrate. However, no significant response to the supply of metals was found in activity tests with acetate or H2/CO2 as the substrates. The trace metals initially presented in each of the granular sludge inocula used are sufficient for attaining the optimal activity on acetate and H2/CO2 for all four sludges tested (Zandvoort et al., 2006b).
Bioreactor studies indicate that metal supplementation improves in most cases the reactor efficiency, mainly measured as the increase of methane production. However, metal supplementation to anaerobic wastewater treatment systems has not yet been systematically researched (Table 3). Moreover, the approaches used to study metal supplementation are hardly comparable. Nutrient supply has also been studied at different temperatures, ranging from 7 C (Li et al., 2007) up to 55 C (Paulo et al., 2004). Different reactor configurations have been used in these studies: such as UASB reactors (Espinosa et al., 1995; Shen et al., 1993), fed-batch UASB sludges (Sharma and Singh, 2001), anaerobic download fixed film reactors (Murray and Van den Berg, 1981), anaerobic film expanded bed reactors (Kelly and Switzenbaum, 1984), upflow flocculent sludge reactors (Callander and Barford, 1983) or continuous stirrer tank reactors (Percheron et al., 1997). Also different substrates have been fed to these metal supplementation studies, including volatile fatty acids (Hoban and Van Den Berg, 1979; Shen et al., 1993; Speece et al., 1983),
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Table 2 Toxic concentrations of cobalt, nickel and zinc in methanogenesis processes. Metal Organism Reactor / technique
Anaerobic toxicity bioassays
Toxic concentration
Up to 35400 mg L 1 (no detectable inhibition) 600800 mg L 1 (717% inhibition) 950 mg L 1 (100% inhibition) 120 g g dry matter 1
Conditions
The sludge was fed with nutrients and acetate or glucose as the sole carbon source under oxygenfree condition at 35 1 C.
Reference
Bhattacharya et al. (1995)
Cobalt Mixed anaerobic sludge
15-day-old wet slurry from digested cattle manure Nickel Anaerobic granular sludge
Batch bottles
The experiment was performed at 37 C.
Jain et al. (1992)
UASB reactor
Anaerobic starchUASB degrading granules reactor Anaerobic granular UASB sludge reactor
Zinc
Anaerobic granular sludge from labscale UASB reactor Anaerobic granular sludge from labscale UASB reactor
UASB reactor Batch bottles
Anaerobic granular Batch sludge from labbottles scale UASB reactor
The reactor was continuously fed with synthetic wastewater composing starch as the sole organic carbon source. 81 mg L 1 (50% inhibition, bed The reactors were treating winery wastewater and sludge) were acclimated in a 13.5-liters UASB reactor at 35 1 C. The HRT was 1 day and the acclimation period 78 mg L 1 (50% inhibition, blanket sludge) for the seed sludge was six months. Granules were sample from four UASB reactors at 118 mg L 1 L (IC50) COD loading rate of 10 g COD L 1 d 1 for over six months at 37 C. 690 mg L 1 (50% inhibition of The experiment was performed at 35 1 C methanogenic activity with Winery wastewater as substrate. sludge operated at HRT 1 day) 270 mg L 1 (50% inhibition of methanogenic activity with sludge operated at HRT 2 day) The experiment was performed at 37 1 C 96 mg L 1 (50% inhibition of methanogenic activity) Starch synthetic wastewater as substrate.
81 mg L 1 (50% inhibition of VFA degradation) 440 mg L 1 (50% inhibition of VFA degradation) 118 mg L 1 (IC50 or 50% inhibition of SMA)
The digesters were acclimated in a 13.5-liter UASB reactor at 35 1 C. The HRT was 1 and 2 days.
Lin and Chen (1999)
Fang and Hui (1994) Lin and Chen (1997)
Fang (1997)
Lin and Chen (1999)
Fang (1997)
UASB reactor: Upflow anaerobic sludge bed reactor. CSTR: Completely stirred tank reactor.
sulfate laden organics (Patidar and Tare, 2006), cane molasses stillage (Espinosa et al., 1995), methanol (Florencio et al., 1993), food industry wastewater (Oleszkiewicz and Romanek, 1989), distillery wastewater (Sharma and Singh, 2001), bean wastewater (Murray and Van den Berg, 1981), whey (Kelly and Switzenbaum, 1984), sugar cane fermentation waste (Callander and Barford, 1983) or molasses wastewater (Percheron et al., 1997).
dosing protocols is that high amounts of cobalt are lost with the effluent.
5.3.3.
Chemical species to be dosed
5.3.2.
Dosing protocol
In continuous methanol fed UASB reactors, cobalt supplementation is required to maintain a high SMA, and therefore, to prevent reactor acidification (Zandvoort et al., 2003). Different cobalt dosing strategies have been studied in methanol fed UASB reactors: continuous addition of a low CoCl2 concentration to a methanol fed UASB reactor only slightly enhanced the SMA of the sludge (Zandvoort et al., 2002a). The same author studied the possibility of pre-loading sludge by pre-incubating the inoculum in a 1 mM CoCl2 solution for 24 hours. Pre-loading clearly overcame cobalt limitation in the methanol fed UASB reactor (Zandvoort et al., 2004). Pulse dosing of cobalt increased the SMA with methanol as the substrate 4 times, clearly overcoming cobalt limitation (Zandvoort et al., 2004). A drawback of these
Repeated pulse addition of low amounts of cobalt is an efficient dosing strategy to maintain a stable methanogenic methanol fed UASB reactor. Pulse addition of cobalt (5 moles cobalt per litre of reactor volume) in the form of CoCl2 creates a pool of cobalt in the granular sludge matrix due to the high cobalt retention (around 90%). In contrast, a much smaller cobalt pool is formed when cobalt is dosed as Co-EDTA2: only 8% of the supplied CoEDTA2 is retained (Fermoso et al., 2008a). Additionally, cobalt wash-out was much less compared to the pulse addition of high amounts of cobalt or the pre-loading cobalt strategies reported in previous studies with methanol fed UASB reactors. The cobalt pool formed upon CoCl2 dosing was enough to keep stable 1 for more than methanogenesis at an OLR of 8.5 g COD L 1 reactor d 15 days between the pulses. Additionally, pulse addition of CoCl2 presents several advantages compared to Co-EDTA2. First of all, as cobalt added as chloride is much more retained in the granular sludge compared to cobalt bound to EDTA, its addition frequency would be much lower, i.e. once per 15 days for CoCl2 versus once per 7 days for Co-EDTA2. The side-effects that EDTA
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Table 3 Stimulation of biological conversions in anaerobic bioreactors by metal supply. Supplied metal
Fe Fe Ni, Co and Fe Trace metals Ni Ni, Co and Fe Co
Reactor
CSTR Upflow flocculent sludge reactor Fed-Batch pHstat Anaerobic film expanded bed reactor Poultry waste digester UASB reactor
Temperature pH (C)
35 36
Substrate
Acetate
Effect upon metal addition OLR (g CODL 1d 1)

0.25 0.750 4.3 Increase acetate removal
Reference
7.55 Cane fermentation waste 6.6 Acetate 6.9 Whey
20, 25, 30 and 35 50 35
7.5
Chicken manure 15
6.9 Food industry 7.3 wastewater 6.8 6.8 7.8 Methanol Volatile fatty acids
UASB reactor
30 35 35 35 35 30 55 725
8.5 11 21.5 2 5.9 20 4.38.9
Ni, Co UASB reactor and Fe Ni, Co UASB reactor and Mo Co and Fe CSTR Ni, Co and Fe Co Co Trace metals Fed-batch granular sludge UASB reactor UASB reactor UASB reactor
Cane molasses stillage 7.8 Molasses wastewater 6.7 Distillery 7.5 wastewater 7.0 Methanol Methanol High concentrated organic wastewater
Hoban and Van Den Berg (1979) Increase acetate removal Callander and Barford (1983) Increase acetate removal Speece et al. (1983) Increase COD removal Kelly and Switzenbaum (1984) Increase biogas formation Williams et al. (1986) Faster sludge growth and Oleszkiewicz better sludge retention. and Romanek Increase in COD removal (1989) Increase COD removal Florencio et al. (1993) Increase COD removal Shen et al. (1993) Increase COD removal Espinosa et al. (1995) Improve anaerobic digestion Percheron et al. (1997) Improve methanogenic activity Sharma and Singh (2001) Increase SMA and methanol Zandvoort et removal al. (2004) High activity of methanogens Paulo et al. (2004) Increase VFA removal Li et al. (2007)
UASB reactor: Upflow anaerobic sludge bed reactor. CSTR: Completely stirrer tank reactor.
causes damage to the granular sludge matrix and to the microbial cells (Fermoso et al., 2008a) make EDTA an unreliable ligand to use in full scale applications that require trace metal supplementation. There are several ligands that could be even more effective than chloride, such as vitamin B12, a complex organic macromolecule with a cobalt ion as the catalytic centre, which has been shown to enhance the methanogenesis of carbon tetrachloride (Guerrero-Barajas and Field, 2005).
5.3.5.
Timing of dosing
5.3.4.
Quantity to be dosed
Calculation of the required amount of cobalt needed per day to support adequate methanogenesis is very important for practice. With the data provided by Fermoso et al. (2008a), the calculation of the mg of cobalt needed to be dosed per litre of reactor and per day was obtained empirically. Considering a stable methanol removal period of 15 days after the CoCl2 1 pulse addition and an OLR of 8.5 g COD L 1 reactor d , the required 1 1 cobalt amounted to 0.36 mol Lreactor d of CoCl2. In case of a Co-EDTA2 pulse, considering a stable methanol removal period of 7 days upon the pulse, the required cobalt amounted 1 of CoCl2. In a methanol fed UASB to 0.77 mol L 1 reactor d 1 reactor with an OLR of 2.6 g COD L 1 reactor d , Zandvoort et al. d 1 would be required (2002a) estimated that 0.15 mol L 1 reactor to maintain a stable methanol removal capacity when CoCl2 was supplied continuously.
Fermoso et al. (2008a) showed that cobalt addition to cobaltlimited methanol fed reactors has to be done before accumulation of volatile fatty acids (VFA) in the effluent. If the addition is done after VFA accumulation, the VFA accumulation will actually be enhanced and reactor acidification will occur (Fig. 4A). Fermoso et al. (2008a) have also shown that the addition of methanol before VFA accumulation in a methanol-fed UASB reactor enhanced methanogenesis. Therefore, a rational timing of the cobalt addition as studied by (Fermoso et al., 2008a) has to be implemented in the strategies of metal addition for full-scale anaerobic bioreactors.
6.
6.1.
Future perspectives
Mechanistic model of metal dynamics
A much more accurate quantification of the required amount and dosing time of cobalt to be dosed can be obtained when a mechanistic model for the CoCl2 dosing to methanol fed UASB reactors is developed. The mechanistic modelling of the cobalt uptake rate is, however, rather complicated because of the complexity of the system under study, where the relation between chemical speciation, biological uptake, biomass
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Table 4 Future research directions to improve the trace metal supplementation to UASB and anaerobic biofilm reactors. Improvement in the characterization of
Metalmicrobe interactions To image the concentration of trace metals in living cells in real time. Element distribution in cells and biofilm sections.
Tool
Fluorescence microscopy with advanced fluorescent probes that bind transition metal ions with high affinity and selectivity. Sub-micrometer spatial resolution and picogram-level sensitivity owing to advances in laser ablation MS, ion beam and synchrotron radiation X-ray fluorescence microprobes. Speciation of elements in microsamples in complex Nanoflow chromatography and capillary electrophoresis coupled with element biological environment as the anaerobic granular sludge. specific ICP MS and molecule-specific electrospray MS/MS and MALDI. Metalsbiofilm interactions To identify and to determine in situ the relative amounts of functional sulfur species down to low concentrations providing information about the oxidation state, fingerprint speciation of metal sites and metal-site structures. Non-invasively monitor metal transport processes and biomass accumulation and distribution. Determination of cobalt taken up into the cell.
EXAFS and XANES, owing to the use of more intense synchrotron beams and efficient focusing optics, offers a unique non-destructive tool.
Nuclear magnetic resonance (NMR) methods. Mapping radioactive metal isotopes previously supplied to the anaerobic granule.
Metalsliquid phase interactions To study the dissolved metal speciation.
Techniques using semi permeable gels, such as DET, DGT or SOFIE. Techniques using selective membranes, such as DMT (charge selective), and PLM (ion selective). Dynamic electrochemical techniques, such as voltammetries and (S)SCP for metals that can amalgamate with mercury, or certain types of microelectrodes. Combinations, such as GIME (porous gel in combination with voltammetry), CGIME (a GIME with a layer of metal binding resin) or certain types of microelectrodes.
MetalsUASB interactions Trace metal source with a defined flux over the UASB. To minimize the metal losses by manipulating the cobalt dissolution rate. Inclusion of trace metal measurement on the reactor system as a controlled parameter. Implementation of metal pulse dosing as manipulated parameter in process control algorithms.
The DMT in a reversed set-up. The sensor and the dosing are then combined in one unit. Cobalt in slow release capsules. Electrochemical release of cobalt. Electrochemical sensors for trace metal analysis in water, using either microlithographically fabricated- or screen-printed microelectrode arrays. Process control can alleviate fluctuations in metal loading rates and subsequently increase the efficiency of anaerobic wastewater treatment plants.
growth, hydrodynamics of the reactor and biofilm characteristics has to be taken into account (Jansen, 2004). Some of these aspects are described in the literature for biofilm systems other than granular sludge (Arican et al., 2002; Flemming, 1995; Flynn, 2003; Wang et al., 2003; Weng et al., 2003; Worms et al., 2006), but the aspects of greatest importance, i.e. chemical interactions between cobalt and the granular sludge matrix, as well as cobalt uptake and biomass growth kinetics are not yet quantified (Van Hullebusch et al., 2003), which hampers the development of these models.
6.2.
Metal dynamics in living cells
An important prerequisite for further understanding of the metal dynamics in living cells is the ability to image the concentration of trace metals in living cells in real time (Table 4). Fluorescence microscopy is ideally suited for this purpose, and the development of fluorescent probes that bind transition metal ions with high affinity and selectivity has recently become an area of active research (Van Dongen et al., 2006), and can contribute to depict
the metal-microorganism interaction at single cell level in the biofilm system. Imaging of the element distribution in cells and biofilm sections is becoming possible with sub-micrometer spatial resolution and picogram-level sensitivity owing to advances in laser ablation MS (Mass Spectrometry), ion beam and synchrotron radiation X-ray fluorescence microprobes (Gordon et al., 2008). Progress in nanoflow chromatography and capillary electrophoresis coupled with element specific ICP MS (Saba et al., 2007; Schaumlffel, 2007) and molecule-specific electrospray MS/MS and Matrix-assisted laser desorption/ionization (MALDI) (Tharamani et al., 2008) enables speciation of elements in microsamples in complex biological environment as the anaerobic granular sludge.
6.3. Metal dynamics and solid state speciation in anaerobic granular sludge
The increasing sensitivity of EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge
3663
Structure), owing to the use of more intense synchrotron beams and efficient focusing optics, offers a unique nondestructive tool to identify and to determine in situ the relative amounts of functional sulfur species down to low concentrations providing information about the oxidation state, fingerprint speciation of metal sites and metal-site structures (Jalilehvand, 2006; Lobinski et al., 2006). The application of more elaborate sulfur extraction schemes for anaerobic granular sludge, yielding more specific fractions including elemental sulfur and disulfides (Canheld et al., 1998; Van der Veen, 2004), which have been successfully applied to freshwater and marine sediments, can also contribute to a better characterization of the sulfur pool in anaerobic granular sludge. Nuclear magnetic resonance (NMR) methods provide the ability to non-invasively monitor metal transport processes and biomass accumulation and distribution (Seymour et al., 2007). The further determination of cobalt taken up into the cell, e.g. by mapping radioactive metal isotopes previously supplied to the anaerobic granule, is another way to better characterize this metal fraction (Lombi et al., 2001).
6.4.
Analytical methods for speciation analysis
For studying the dissolved metal speciation, the low metal concentrations and properties of the medium of anaerobic bioreactors set very specific demands on the experimental techniques chosen (Table 4). In general, a number of methods is available, including: techniques using semi permeable gels, such as diffusive equilibrium thin films (Bottrell et al., 2007), diffusion gradient in thin films (Davison and Zhang, 1994), sediment or fauna incubation experiment technique (Vink, 2002); Techniques using selective membranes, such as DMT (charge selective) (Temminghoff et al., 2000), and permeation liquid membrane (ion selective) (Parthasarathy et al., 2003); dynamic electrochemical techniques, such as voltammetries (Buffle and Tercier-Waeber, 2005) and stripping chronopotentiometry at scanned deposition potential (Van Leeuwen and Town, 2003) for metals that can amalgamate with mercury; combinations, such as gel integrated microelectrodes (GIME) (porous gel in combination with voltammetry) or CGIME (a GIME with a layer of metal binding resin) (Buffle and Tercier-Waeber, 2005). Jansen et al. (2005) assessed the applicability of Competitive Ligand Exchange Adsorptive Stripping Voltammetry (CLEAdSV) to analyze cobalt and nickel speciation in anaerobic bioreactor media. This technique has the advantages of selective detection of both cobalt and nickel at low concentrations and the possibility of analyzing strong binding properties. It combines bulk equilibrium ligand exchange with a two-step electrochemical technique. Jansen et al. (2005) presented linear calibration for both cobalt and nickel in anaerobic media down to ca. 1 nM using CLE-AdSV and demonstrated the suitability of the technique for distinguishing between strongly bound and loosely bound/free fractions of metals.
membrane with a nutrient solution, buffered by the addition of a strong ligand, the free ion activity of the reactor solution can be controlled. The DMT cell can also be used as a trace metal source with a defined flux over the membrane surface. The sensor and the dosing are then combined in one unit, which is a very elegant solution. Other kinds of cobalt dosing strategies that minimize the metal losses by manipulating the cobalt dissolution rate can be developed in further research, e.g. including cobalt in slow release capsules (Im et al., 2005) or electrochemical release of cobalt (Cosnier et al., 1994) (Table 4). Electrochemical sensors have been developed for trace metal analysis in water, using either microlithographically fabricatedor screen-printed microelectrode arrays (Nol et al., 2006; Xie et al., 2005). The sensors are chiefly based on the principles of stripping voltammetry (anodic, cathodic, and adsorptive voltammetry) and stripping potentiometry (Ostapczuk, 1993). The combination of microelectrodes and computer-controlled miniaturized instrumentation is very suitable for the development of portable analytical instruments for in situ and on-site measurement of heavy metals in reactors (Xie et al., 2005). The inclusion of trace metal measurement in the reactor system as a controlled parameter will allow to implement metal dynamics in process control design. Different applicable control strategies include feedforward, supervisory, multivariable and adaptative control features as well as sophisticated digital logic control (Stephanopoulos, 1984). The implementation of metal pulse dosing as manipulated parameter in such process control algorithms can compensate process disturbances, such as variation in incoming flows, wastewater characteristics or temperature. Process control can thus alleviate fluctuations in metal loading rates and subsequently increase the efficiency of anaerobic wastewater treatment plants.
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S CI EN CE OF T H E T OTAL EN V I RO N M EN T 4 0 7 ( 2 0 09 ) 36 5 2 3 66 7

Metal supplementation to UASB bioreactors: from cell-metal interactions to full-scale application

Hydrogenase Formate dehydrogenase Superoxide dismutase

Nitrogenase Chloroperoxydase Bromineperoxydase

Metal uptake into the cell

Metal toxicity in granular sludge

Liquid phase speciation

Metalsliquid phase interaction

Kinetics of precipitation and complex formation

Metal limitation in UASB reactors Methanol fed bioreactors

Metal toxicity in bioreactors

Metal dosing Metal dosing requirements

Other substrates in anaerobic bioreactors

Cobalt Mixed anaerobic sludge

The experiment was performed at 37 C.

Jain et al. (1992)

UASB reactor Batch bottles

Anaerobic granular Batch sludge from labbottles scale UASB reactor

Lin and Chen (1999)

Fang and Hui (1994) Lin and Chen (1997)

Lin and Chen (1999)

Chemical species to be dosed

Effect upon metal addition OLR (g CODL 1d 1)

7.55 Cane fermentation waste 6.6 Acetate 6.9 Whey

20, 25, 30 and 35 50 35

8.5 11 21.5 2 5.9 20 4.38.9

Metalsliquid phase interactions To study the dissolved metal speciation.

Metal dynamics in living cells

Analytical methods for speciation analysis

Process monitoring and control

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