A deeper insight into the complex processes involved in this field, covering the biological, chemical and engineering fundamentals needed to further develop effective methodologies.
The book devotes detailed chapters to each of the four main areas of environmental biotechnology -- wastewater treatment, soil treatment, solid waste treatment, and waste gas treatment -- dealing with both the microbiological and process engineering aspects.
The result is the combined knowledge contained in the extremely successful volumes 11a through 11c of the "Biotechnology" series in a handy and compact form.
"synopsis" may belong to another edition of this title.
Hans-Joachim Jordening gained his chemistry degree in 1984, his doctorate three years later and his lecturing qualification in 2000. He has been at the TU Brunswick since 1987, heading the Department of Microbiology and Wastewater Technology from 1992 to 1997. His research interests include biological methods of wastewater purification, the enzymatic modification of saccharides, and modeling biocatalytic processes.
Josef Winter earned his doctorate in 1974, and was a post-doc at MIT before gaining his lecturing qualification in 1980. He has been Professor of Waste Water Management and head of the Institute of Biology for Biological Engineering and Biotechnology of Wastewater Treatment at the TU Karlsruhe since 1993. His research includes physiology of aerobic and anaerobic degradation, wastewater and waste treatment processes, and soil remediation.
A deeper insight into the complex processes involved in this field, covering the biological, chemical and engineering fundamentals needed to further develop effective methodologies.
The book devotes a detailed chapter to each of the four main areas of environmental biotechnology -- wastewater treatment, soil treatment, solid waste treatment, and waste gas treatment -- dealing with both the microbiological and process engineering aspects.
A deeper insight into the complex processes involved in this field, covering the biological, chemical and engineering fundamentals needed to further develop effective methodologies.
The book devotes a detailed chapter to each of the four main areas of environmental biotechnology -- wastewater treatment, soil treatment, solid waste treatment, and waste gas treatment -- dealing with both the microbiological and process engineering aspects.
Claudia Gallert and Josef Winter
1.1 Introduction
Water that has been used by people and is disposed into a receiving water body with altered physical and/or chemical parameters is defined as wastewater. If only the physical parameters of the water were changed, e.g., resulting in an elevated temperature after use as a coolant, treatment before final disposal into a surface water may require only cooling close to its initial temperature. If the water, however, has been contaminated with soluble or insoluble organic or inorganic material, a combination of mechanical, chemical, and/or biological purification procedures may be required to protect the environment from periodic or permanent pollution or damage. For this reason, legislation in industrialized and in many developing countries has reinforced environmental laws that regulate the maximum allowed residual concentrations of carbon, nitrogen, and phosphorous compounds in purified wastewater, before it is disposed into a river or into any other receiving water body However, enforcement of these laws is not always very strict. Enforcement seems to be related to the economy of the country and thus differs significantly between wealthy industrialized and poor developing countries. In this chapter basic processes for biological treatment of waste or wastewater to eliminate organic and inorganic pollutants are summarized.
1.2 Decomposition of Organic Carbon Compounds in Natural and Manmade Ecosystems
Catabolic processes of microorganisms, algae, yeasts, and lower fungi are the main pathways for total or at least partial mineralization/decomposition of bioorganic and organic compounds in natural or manmade environments. Most of this material is derived directly or indirectly from recent plant or animal biomass. It originates from carbon dioxide fixation via photosynthesis (-> plant biomass), from plants that served as animal feed (-> detritus, feces, urine, etc.), or from fossil fuels or biologically or geochemically transformed biomass (-> peat, coal, oil, natural gas). Even the carbon portion of some xenobiotics can be tracked back to a biological origin, i.e., if these substances were produced from oil, natural gas, or coal. Only because the mineralization of carbonaceous material from decaying plant and animal biomass in nature under anaerobic conditions with a shortage of water was incomplete, did the formation of fossil oil, natural gas, and coal deposits from biomass occur through biological and/or geochemical transformations. The fossil carbon of natural gas, coal, and oil enters the atmospheric C[O.sub.2] cycle again as soon as these compounds are incinerated as fuels or used for energy generation in industry or private households.
Biological degradation of recent biomass and of organic chemicals during solid waste or wastewater treatment proceeds either in the presence of molecular oxygen by respiration, under anoxic conditions by denitrification, or under anaerobic conditions by methanogenesis or sulfidogenesis. Respiration of soluble organic compounds or of extracellularly solubilized biopolymers such as carbohydrates, proteins, fats, or lipids in activated sludge systems leads to the formation of carbon dioxide, water, and a significant amount of surplus sludge. Some ammonia and [H.sub.2]S may be formed during degradation of sulfur-containing amino acids or heterocyclic compounds. Oxygen must either be supplied by aeration or by injection of pure oxygen. The two process variant for oxygen supply differ mainly in their capacity for oxygen transfer and the stripping efficiency for carbon dioxide from respiration. Stripping of carbon dioxide is necessary to prevent a drop in pH and to remove heat energy. Respiration in the denitrification process with chemically bound oxygen supplied in the form of nitrate or nitrite abundantly yields dinitrogen. However, some nitrate escapes the reduction to dinitrogen in wastewater treatment plants and contributes about 2% of the total [N.sub.2]O emissions in Germany (Schn et al., 1994). Denitrifiers are aerobic organisms that switch their respiratory metabolism to the utilization of nitrate or nitrite as terminal electron acceptors, if grown under anoxic conditions. Only if the nitrate in the bulk mass has been used completely does the redox potential become low enough for growth of strictly anaerobic organisms, such as methanogens or sulfate reducers. If anaerobic zones are allowed to form in sludge flocs of an activated sludge system, e.g., by limitation of the oxygen supply, methanogens and sulfate reducers may develop in the center of sludge flocs and form traces of methane and hydrogen sulfide, found in the off-gas.
Under strictly anaerobic conditions, soluble carbon compounds of wastes and wastewater are degraded stepwise to methane, C[O.sub.2], N[H.sub.3], and [H.sub.2]S via a syntrophic interaction of fermentative and acetogenic bacteria with methanogens or sulfate reducers. The complete methanogenic degradation of biopolymers or monomers via hydrolysis/fermentation, acetogenesis, and methanogenesis can proceed only at a low [H.sub.2] partial pressure, which is maintained mainly by interspecies hydrogen transfer. Interspecies hydrogen transfer is facilitated when acetogens and hydrogenolytic methanogenic bacteria are arranged in proximity in flocs or in a biofilm within short diffusion distances. The reducing equivalents for carbon dioxide reduction to methane or sulfate reduction to sulfide are derived from the fermentative metabolism, e.g., of clostridia or Eubacterium sp., from oxidation of fatty acids, or the oxidation of alcohols. Methane and C[O.sub.2] are the main products in anaerobic environments where sulfate is absent, but sulfide and C[O.sub.2] are the main products if sulfate is present.
1.2.1 Basic Biology, Mass, and Energy Balance of Aerobic Biopolymer Degradation
To make soluble and insoluble biopolymers - mainly carbohydrates, proteins, and lipids - accessible for respiration by bacteria, the macromolecules must be hydrolyzed by exoenzymes, which often are produced and excreted only after contact with respective inductors. The exoenzymes adsorb to the biopolymers and hydrolyze them to monomers or at least to oligomers. Only soluble, low molecular weight compounds (e.g., sugars, disaccharides, amino acids, oligopeptides, glycerol, fatty acids) can be taken up by microorganisms and be metabolized for energy production and cell multiplication.
Once taken up, degradation via glycolysis (sugars, disaccharides, glycerol), hydrolysis and deamination (amino acids, oligopeptides), or hydrolysis and oxidation (phospholipids, long-chain fatty acids) proceeds in the cells. Metabolism of almost all organic compounds leads to the formation of acetyl-CoA as the central intermediate, which is used for biosyntheses, excreted as acetate, or oxidized to C[O.sub.2] and reducing equivalents in the tricarboxylic acid (TCA) cycle. The reducing equivalents are respired with molecular oxygen in the respiration chain. The energy of a maximum of only 2 mol of anhydridic phosphate bonds of ATP is conserved during glycolysis of 1 mol of glucose through substrate chain phosphorylation. An additional 2 mol of ATP are formed during oxidation of 2 mol of acetate in the TCA cycle, whereas 34 mol ATP are formed by electron transport chain phosphorylation with oxygen as the terminal electron acceptor. During oxygen respiration, reducing equivalents react with molecular oxygen in a controlled combustion reaction.
When carbohydrates are respired by aerobic bacteria, about one third of the initial energy content is lost as heat, and two thirds are conserved biochemically in 38 phosphoanhydride bonds of ATP. In activated sludge reactors or in wastewater treatment ponds that are not loaded with highly concentrated wastewater, wall irradiation and heat losses with the off-gas stream of aeration into the atmosphere prevent self-heating. In activated sludge reactors for treatment of highly concentrated wastewater, however, self-heating up to thermophilic temperatures may occur if the wastewater is warm in the beginning, the hydraulic retention time for biological treatment is short (short aeration time), and the air or oxygen stream for aeration is restricted so as to supply just sufficient oxygen for complete oxidation of the pollutants (small aeration volume).
The conserved energy in the terminal phosphoanhydride bond of ATP, formed during substrate chain and oxidative phosphorylation by proliferating bacteria is partially used for maintenance metabolism and partially for cell multiplication. Partitioning between both is not constant, but depends on the nutritional state. In highly loaded activated sludge reactors with a surplus or at least a non-growth-limiting substrate supply, approximately 50% of the substrate is respired in the energy metabolism of the cells and 50% serves as a carbon source for cell growth (Table 1.1). The biochemically conserved energy must be dissipated to be used for the maintenance metabolism of existing cells and cell growth.
If the substrate supply is growth-limiting, e.g., in a low-loaded aerobic treatment system, a higher proportion of ATP is consumed for maintenance, representing the energy proportion that bacteria must spend for non-growth-associated cell survival metabolism, and less energy is available for growth. Overall, more of the substrate carbon is respired, and the ratio of respiration products to surplus sludge formed is higher, e.g., around 70% : 30% (Table 1.1). In a trickling filter system, an even higher proportion of the substrate seems to be respired. This might be due to protozoa grazing off part of the biofilm.
For comparison, Table 1.1 also summarizes carbon dissipation in anaerobic methanogenic degradation. Only about 5% of the fermentable substrate is used for cell growth (surplus sludge formation) in anaerobic reactors, whereas 95% is converted to methane and C[O.sub.2], and most of the energy of the substrates is conserved in the fermentation products.
1.2.1.1 Mass and Energy Balance for Aerobic Glucose Respiration and Sewage Sludge Stabilization
In most textbooks of microbiology, respiration of organic matter is explained by Eq. 1, with glucose used as a model substance. Except for an exact reaction stoichiometry of the oxidative metabolism, mass and energy dissipation, if mentioned at all, are not quantified. Both parameters are, however, very important for activated sludge treatment plants. The surplus sludge formed during wastewater stabilization requires further treatment, causes disposal costs, and - in the long run - may be an environmental risk, and heat evolution during unevenly high-loaded aerobic treatment may shift the population toward more thermotolerant or thermophilic species and thus, at least for some time, may decrease the process efficiency.
1 mol [C.sub.6][H.sub.12][O.sub.6] + 6 mol [O.sub.2] -> 6 mol C[O.sub.2] + 6 mol [H.sub.2]O + heat energy (1)
If 1 mol of glucose (MW = 180 g) is degraded in an activated sludge system at a high BOD loading rate (e.g., >0.6 kg [m.sup.-3] [d.sup.-1] BOD), approximately 0.5 mol (90 g) is respired to C[O.sub.2] and water, with consumption of 3 mol of [O.sub.2] (96 g), releasing 19 mol of ATP (Fig. 1.1). The other 0.5 mol of glucose (90 g) is converted to pyruvate by one of three glycolytic pathways, accompanied by the formation of 0.5-1 mol ATP. Pyruvate or its subsequent metabolic products, e.g., acetate or dicarboxylic acids, are directly used as carbon substrates for cell multiplication and surplus biomass formation. A maximum amount of 20 mol ATP is thus available for growth and maintenance (Fig. 1.1). At a pH of 7, about 44 kJ of energy is available for growth per mol of ATP hydrolyzed to ADP and inorganic phosphate (Thauer et al., 1977). For an average molar growth yield of aerobes of 4.75 g per mol ATP (Lui, 1998), 90 g biomass can be generated from 180 g glucose. If the combustion energy per g of cell dry mass is 22 kJ, about 890 kJ (2870-980 kJ) is lost as heat during respiration (Fig. 1.1). The energy loss is the sum of heat losses during respiration and cell growth.
At a low BOD loading rate, the proportion of glucose respired in relation to the proportion of glucose fixed as surplus biomass can shift. Up to 0.7 mol (126 g) of glucose can be oxidized to C[O.sub.2], requiring 4.2 mol of oxygen (134.4 g [O.sub.2]). Thus, for respiration of 1 mol of glucose, different amounts of oxygen may be consumed, depending on the loading rate of the wastewater treatment system and the different amounts of carbon dioxide and of surplus sludge formed (Fig. 1.1, Table 1.1).
The energy and carbon balance deduced above can be analogously applied to aerobic stabilization of raw sewage sludge. If the initial dry matter content is around 36g [L.sup.-1] (average organic dry matter content of sewage sludge) and if a biodegradability of 50% within the residence time in the sludge reactor is obtained, about 9 g [L.sup.-1] of new biomass is formed, and thus 27 g [L.sup.-1] (36 - 18 + 9) remains in the effluent.
The released heat energy is approximately 89 kJ [L.sup.-1] of reactor content. To estimate the theoretical temperature rise, this amount of heat energy must be divided by 4.185 kJ (specific energy requirement for heating 1 L of [H.sub.2]O from 14.5-15.5C). Thus, by respiration of 18 g [L.sup.-1] organic dry matter, the reactor temperature increases by 21.3C within the residence time required for degradation ([less than or equal to]16 h), provided that no heat energy is lost. A great proportion of the heat energy is, however, transferred via the liquid phase to the aeration gas and stripped out, whereas a smaller proportion is lost through irradiation from the reactor walls. Since air, containing almost 80% nitrogen, is normally used as an oxygen source in aeration ponds or activated sludge reactors, the heat transfer capacity of the off-gas is high enough to prevent a significant increase in the wastewater temperature. Thus, ambient or at least mesophilic temperatures can be maintained. An increasing temperature of several degrees Celsius would lead to a shift in the population in the reactor and - at least temporarily - would result in reduced process stability, but an only slightly increased temperature of a few degrees Celsius might simply stimulate the metabolic activity of the prevalent mesophilic population. In practice, in activated sewage sludge systems no self-heating is observed because degradability is only about 50% and complete heat transfer to the atmosphere occurs via the off-gas at a retention time of more than 0.5 d. If, however, wastewater from a dairy plant or a brewery with a similar COD concentration, but with almost 100% biodegradable constituents, is stabilized with pure oxygen, twice as much heat evolves, leading to a theoretical temperature rise of 57 C. Self-heating is observed, since there is much less off-gas and the heat loss is thus significantly lower. In addition, due to higher reaction rates than with sewage sludge, the heat is generated during a shorter time span (shorter retention time).
1.2.1.2 Mass and Energy Balance for Anaerobic Glucose Degradation and Sewage Sludge Stabilization
For anaerobic wastewater or sludge treatment, oxygen must be excluded to maintain the low redox potential that is required for survival and metabolic activity of the acetogenic, sulfidogenic, and methanogenic populations. Hydrolysis of polymers, uptake of soluble or solubilized carbon sources, and the primary metabolic reactions of glycolysis up to pyruvate and acetate formation seem to proceed identically or at least analogously in aerobic and anaerobic bacteria. Whereas aerobes oxidize acetate in the TCA cycle and respire the reducing equivalents with oxygen, anaerobes, such as Ruminococcus sp., Clostridium sp., or Eubacterium sp., either release molecular hydrogen or transform pyruvate or acetate to highly reduced metabolites, such as lactate, succinate, ethanol, propionate, or n-butyrate. For further degradation within the anaerobic food chain, these reduced metabolites must be oxidized anaerobically by acetogenic bacteria. Since the anaerobic oxidation of propionate or n-butyrate by acetogenic bacteria is obligately accompanied by hydrogen production but is only slightly exergonic under conditions of a low [H.sub.2] partial pressure (Bryant, 1979), acetogens can grow only when hydrogen is consumed by hydrogen-scavenging organisms such as methanogens or sulfate reducers.
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