ENVIRONMENTAL IMPACTS OF EMISSIONS AND ASH FROM BIOSOLIDS INCINERATION INTRODUCTION Incineration and pyrolysis are thermal-chemical processes that reduce the amount (weight and volume) of waste and sterilize solids. (Pyrolysis is similar to incineration, except that it involves burning in the absence of oxygen; this process typically occurs in a fluidized-bed reactor. Unless noted, this summary uses the term “incineration” to describe both processes.) Incineration also produces energy, emissions, and ash. The quality of the incineration byproducts is related to the quality of the raw materials, operation of the incinerator, and the volatility or combustibility of contaminants in the raw materials. Incineration is a partial biosolids disposal method only, because the ash requires proper disposal. The mass of fly ash produced by incineration is usually between 15 to 45 percent of the mass of the dry biosolids burned (Greenberg et al., 1981). Potential environmental impacts of and concerns regarding incineration include: 1) air pollution from emissions, 2) water pollution from boiler blowdown and scrubber water discharge, 3) decreased effluent quality from recirculating loads, and 4) ash handling and disposal (Dewling, 1980). Denison et al. (1987) even suggested that incinerators could process trash into hazardous waste, because studies have shown that ash can release metals and hazardous organics into the environment. Nevertheless, incineration of biosolids remains an important component of biosolids management programs in the United States. Metals are neither created nor destroyed by incineration; their amounts in biosolids before incineration are identical to those present in the sum of emissions, scrubber water, and ash. Incineration will, however, change the concentration of metals by destroying (combusting) the organic portion of the biosolids (reducing mass). Incineration may also change the form of metals, because complexes are broken down and new ones are created. To meet specific health and regulatory goals for stack emissions, incinerators are increasingly equipped with pollution abatement equipment such as fabric filters, highefficiency electrostatic precipitators (ESPs), and scrubbers. Such devices increase the amount of ash and cause both the concentration and leachability of several trace metals in the fly ash to increase. The following is a summary of the content of various literature on the environmental impacts of emissions and ash from biosolids incineration. The summary is divided into four major sections: 1) system design; 2) regulations; 3) emissions; and 4) ash. For emissions, the literature reviewed was limited to biosolids incinerators only; the section on ash includes literature on municipal incinerators, because the properties and characteristics of ash are similar regardless of the source of the ash. Abstracts of the articles that are referenced in this NBMA Summary—Incineration summary are included and are available for further review by contacting the Northwest Biosolids Management Association. 2 NBMA Summary—Incineration SYSTEM DESIGN The type of incinerator and the pollution abatement equipment at an incinerator both influence the quality of incineration byproducts. This section describes the types of incinerators and pollution abatement equipment found in the United States. Incinerators Approximately 200 biosolids incinerators operate in the United States. Most are multiplehearth incinerators, while most of the remaining incinerators are fluidized-bed incinerators. Multiple-hearth incinerators are seldom installed currently, because fluidized-bed incinerators are less expensive to build and operate, more flexible to operate, and can meet emission requirements without an afterburner (Hemphil, 1988). Multiple-hearth incinerators were originally designed for processing mineral ores and have been used on biosolids since the 1930s (Dykes et al., 1987). The multiple-hearth incinerator is a staged process consisting of 4 to 12 hearths. The upper hearths are used for biosolids drying, combustion occurs in the central hearths, and ash cooling takes place in the lower hearths. An afterburner is sometimes used at the exit of the furnace to reduce hydrocarbon emissions and eliminate odors. The multiple-hearth incinerator produces demister effluent, bottom ash, stack emissions, and a wet scrubber slurry, which yields a fly ash and scrubber water (Fradkin et al., 1987). Fluidized-bed incinerators were originally developed to recover catalysts from oil refining. The first fluidized-bed biosolids incinerator was installed in Lynnwood, Washington in 1961 (Dykes et al., 1987). In 1988, 70 fluidized-bed incinerators burned biosolids in the United States (Hemphil, 1988). A fluidized-bed incinerator has a single combustion chamber in which biosolids drying and combustion occur simultaneously. Combustion occurs in two zones within the chamber: 1) water evaporates and pyrolysis of organics occurs in the bed, and 2) free carbon and combustible gases are burned in the freeboard area above the bed (Dykes et al., 1987). Because its combustion products exit though the top of the furnace, a fluidized-bed incinerator does not produce bottom ash (Fradkin, 1987). Fluidized-bed incinerators operate best at peak capacity and are easily shut down and restarted (Hemphil, 1988). Therefore, they can be operated efficiently without continuous operation. System design of incinerators has been influenced by the development of biosolids dewatering techniques, which reduced the energy required to evaporate the water from the biosolids. However, as pretreatment of biosolids can reduce fuel requirements, it usually requires increased energy in other unit processes (Dewling, 1980). Incinerators are designed to be autogenous; auxiliary fuel, usually natural gas or fuel oil, is used only for startup; burning the organics in the biosolids keeps the fires going. Coincineration (burning biosolids with solid waste) is another means of reducing auxiliary fuel needs. Simple methods of reducing energy requirements through waste heat recovery include using waste heat to preheat incoming air. Waste heat can also be used for heating systems or to produce electricity. Waste heat recovery is economically attractive for communities over 3 NBMA Summary—Incineration 200,000 that co-burn biosolids with municipal solid waste. A community of this size produces approximately 76,000 m3 day-1 wastewater, 82 Mg day-1 biosolids, and 450 Mg day1 burnable refuse. The importance of incinerator maintenance and efficient burning is apparent from a case reported by Wall (1985). The City of Indianapolis, Indiana installed $250,000 worth of instrumentation to improve the efficient operation of its incinerator and has since saved $1,000,000 in fuel and an undetermined amount in operation and maintenance costs annually. The instrumentation helped to regulate excess air and temperatures in the incinerator and improve operation. The incinerator operated at 30 percent of maximum allowable particulate emissions without additional pollution abatement equipment, as compared to 400 percent before the instrumentation was installed. This reduction in emissions was realized merely by improving incinerator efficiency. Incinerators in Nashville, Tennessee, Hartford, Connecticut, and Buffalo, New York are using similar strategies to improve fuel efficiency. Pollution Abatement Equipment The type of pollution abatement equipment used in incinerators is important in determining emissions. Bennett and Knapp (1982) studied four incinerators and found that emissions of cadmium (Cd) were far greater at the incinerator with a wet single-pass scrubber system. This type of system is considerably less efficient for the removal of submicron particles than other scrubber systems. This is particularly important because Cd emissions are predominantly associated with small particles. Before 1978, only 20 percent of all multiple-hearth incinerators were equipped with Venturi/impingement-tray scrubbers, but 14 out of 17 new incinerators built since 1978 used this technology, including a Venturi scrubber followed by impingement-tray scrubber/cooler compartment (Dykes et al., 1987). ESPs and wet scrubbing devices control particles, and wet alkaline scrubbers control acid gases. However, volatile arsenic (As), Cd, lead (Pb), and mercury (Hg) adsorb on fine particles that are difficult to capture (Frost, 1988). A study by Takeda and Hiraoka (1976) found that scrubber water contained relatively high concentrations of trace metals. However, the total amount of metals was quite small compared with the total mass balance. The particulate collection efficiencies of the scrubber for the vaporized trace metals were 0.6 to 2.7 percent for Cd, 0.6 to 1.6 percent for Pb, 0.9 to 2.3 percent for manganese (Mn), 3.9 to 4.7 percent for copper (Cu), and 1.8 to 85 percent for zinc (Zn). Thus, the trace metals were scarcely caught in the scrubber water. REGULATIONS GOVERNING INCINERATION AND ASH DISPOSAL Incineration of biosolids and the disposal of incinerated biosolids ash are covered by various state and federal regulations. 4 NBMA Summary—Incineration Incineration Biosolids incineration must meet the requirements in the federal regulation 40 CFR Part 503 Subpart E, with the following exceptions: • If municipal solid waste accounts for more than 30 percent (by dry weight) of the mixture of biosolids and auxiliary fuel (for example, wood chips, coal, municipal solid waste, grit, scum, and screenings) following incineration, the process is covered by 40 CFR Parts 60 and 61. • Nonhazardous incinerator ash generated during the firing of biosolids is not covered by 40 CFR Part 503 when it is used or disposed. It must be disposed according to the solid waste disposal regulations in 40 CFR Part 258. However, if the ash is applied to land or placed on other than a municipal solid waste landfill, 40 CFR Part 257 must be followed. • Hazardous waste is not considered to be auxiliary fuel under 40 CFR Part 503. Thus, an incinerator that burns hazardous waste with biosolids is considered to be a hazardous waste incinerator and is covered by 40 CFR Parts 261 through 268. Subpart E of the 503 rule covers requirements for biosolids incineration. §503.40 defines Subpart E §503.40 (a) as applying to a person who fires biosolids in a biosolids incinerator, to a biosolids incinerator, and to biosolids fired in a biosolids incinerator. §503.40 (b) applies to the exit gas from a biosolids incinerator stack. Pollutant limits for seven metals— beryllium (Be), Hg, Pb, As, Cd, chromium (Cr), and nickel (Ni)—are regulated by §503.43 (a) through (d). Total hydrocarbon concentration in biosolids emissions is covered in §503.44 (a) and (b). Management practices (§503.45), frequency of monitoring (§503.46), recordkeeping (§503.47), and reporting (§503.48) are also covered. State and local regulations also apply to biosolids incineration and are often more stringent or define biosolids differently than the federal regulation. These other regulations can be obtained at the appropriate state biosolids permitting authorities. In Europe, the Federal Republic of Germany is at the forefront of air pollution control for incinerators, with regulations covering the principles of protection, precaution, minimum residue formation, and waste heat recovery. Specific requirements include flue gas temperature above 800˚ C (not possible in multiple-hearth incinerators) and oxygen content of flue gas at 6 percent. In the United Kingdom, the Economic Commission Directive of 1984 requires incinerators to get approval during the design stage by the appropriate government authority (Frost, 1988). The type of thermal process can also affect emissions and regulatory compliance. Majima et al. (1977) compared noncombustion pyrolysis and partial combustion pyrolysis to incineration and found that HCN, NH3, HCl, and odor evolved in pyrolysis and could be removed in secondary combustion or gas scrubbing. For both pyrolysis processes, the total exhaust gas volume and total fuel required was 67 percent and 65 to 70 percent respectively 5 NBMA Summary—Incineration of that required in incineration. Furthermore, waste scrubbing water was below Japanese drainage water pollutant standards. Testing is typically performed during smooth operations. Metal and organic emissions during startup, shutdown, temperature excursions, feed rate changes, and downtime are rarely tested, but are likely to exceed emissions during smooth operations and emission standards (Dykes et al., 1987). Disposal of Incinerated Ash Disposal of incinerated ash from biosolids incineration is regulated by 40 CFR Parts 257, 258, or 261–268, as appropriate. Data from the EPA and other sources indicate that hazardous levels, as defined by the EPA’s extraction procedure (EP) toxicity test, of Pb, Cd, and other toxic substances have been found in ash. The EP toxicity test identifies the water solubility of metals and the concentration of contaminants in the leachate. Regulations are then based on the results of the test. Regulatory levels for dangerous waste are 5.0 to 500 mg L-1 Pb and 1.0 to 100 mg L-1 Cd; the levels for extremely hazardous waste are greater than 500 mg L-1 Pb and greater than 100 mg L-1 Cd (Knudson, 1986). Washington and California have designated fly ash as hazardous waste that must be disposed of under stricter regulations (Denison et al., 1987). In Washington, fly ash is handled as a dangerous or extremely hazardous waste, while bottom ash is excluded from hazardous waste designation (Knudson, 1986). Knudson (1986) subjected fly and bottom ash samples from seven incinerators in the United States to dangerous waste criteria tests. The tests showed that all five of the fly ash samples were considered to be hazardous waste under federal standards and three samples were considered to be extremely hazardous waste under Washington State standards. None of the bottom ash samples were considered to be hazardous waste under federal standards; however, under Washington State standards, four samples were considered to be dangerous waste and one was extremely hazardous waste, due to the presence of metal carcinogens. The two combined ash samples were considered to be dangerous waste due to metal carcinogens, and one was considered to be hazardous waste, due to Pb concentration. The EPA and the Environmental Defense Fund (EDF) have grown increasingly concerned with the lack of regulatory compliance by incinerator operators concerning hazardous waste and ash disposal. The EDF notified 104 municipal incinerators that they were required to test their ash to determine if it is hazardous under EPA guidelines. The results of Pb and Cd levels from fly ash and combined ash were reported (Denison et al., 1987). Once the testing was completed, it was found that fly ash values exceeded acceptable Cd and Pb limits in all but one case, according to the EP toxicity test. Cd ranged from 2.1 to 100 mg L-1, and Pb ranged from 2.5 to 230 mg L-1 in fly ash (acceptable test limits are 1.0 and 5.0 respectively), and 0.02 to 5.30 mg L-1 Cd and 0.5 to 31.0 mg L-1 Pb in combined ash (Denison et al., 1987). The EDF recommends: 1) testing fly and bottom ash frequently and thoroughly; 2) imposing strict handling, transportation, and disposal methods for all ash; and 3) listing fly ash as a hazardous waste (Denison et al., 1987). 6 NBMA Summary—Incineration The EPA has decided not to publish the technical guidance for ash disposal until the risks of ash are evaluated. The EDF currently has lawsuits pending against municipal incinerators in Chicago and New York, alleging that incinerator ash from these facilities should be considered to be hazardous waste even though the EPA has designated incinerator ash as nonhazardous under the Resource Conservation and Recovery Act (RCRA). EMISSIONS FROM BIOSOLIDS INCINERATION Emissions from incinerators include particulates, water vapor, heat, CO, CO2, SO2, NOx, hydrocarbons, volatile organics, and metals. The concerns over emissions from incinerators include not only the immediate pollution having air quality impacts, but also eventual deposition to plants and soils, leading to potential long-term detrimental effects to the environment. High temperature, humidity, and chlorides are corrosive air pollutants. High chlorine content in biosolids also results in complexation of metals as metal chlorides, which are more soluble in water than other metals (Denison and Silbergeld, 1988). Nitrogen oxides form in most combustion reactions, but are not formed at high enough concentrations to pose emission problems in temperatures below 982˚ C (Dewling, 1980). Blown sand from fluidized-bed incinerators and particulates from both fluidized-bed and multiple-hearth incinerators are erosive (Hemphil, 1988). Particulates above 20 microns can be completely separated from gaseous emissions (Liao and Pilat, 1972). However, smaller particles are not easily captured in pollution abatement equipment and thus enter the environment in emissions. Asbestos fibers have been found in biosolids of several cities. However, asbestos was absent from all ash samples tested by Patel–Mandik et al. (1988), suggesting potential escape in emissions. It is believed that temperatures of 550˚ C or higher dehydroxylate the asbestos lattice, resulting in alteration or destruction of the mineral. Unfortunately, the toxicology associated with altered asbestos structures is unknown. Sulfur oxides are formed by combustion of pyritic and organic sulfur. Although approximately 75 percent of total sulfur content in municipal biosolids is in the form of sulfur oxides, this is usually not a problem in incineration, according to Dewling (1980). Acidic gases (HCl and SO2) are formed in municipal solid waste incinerators, but can be removed effectively by alkali wet scrubbers (Lowe, 1988; Frost, 1988). Trace Metals, Particle Size, and Temperature Emissions of toxic metals from biosolids incinerators can present a risk to human health and the environment (Barton, 1991; Vancil et al., 1991). Barton (1991) examined the behavior of metals in municipal incinerators to identify the mechanisms responsible for metals emissions and to determine the effect of key operating parameters. The primary escape mechanism identified for metals involved the vaporization of metals in the combustion zone and subsequent condensation in the exhaust system. This study found that combustion 7 NBMA Summary—Incineration significantly increased the concentration of toxic metals on submicron particles. Combustion chamber temperatures were found to have a strong effect on metals emissions. No relationship was observed between total particulate emissions and metals emissions. Incineration breaks down the matrix binding trace metals in biosolids, and leaves metals in more soluble and volatile forms (Denison and Silbergeld, 1988; Segall et al., 1992). These metals either remain in ash in soluble forms or are lost from the incinerator in emissions. The emissions of metals from biosolids incinerators are not solely dependent on the quality of the feed biosolids; the emissions also depend on volatility, emission particle size distribution, and incinerator operating temperature. Since metals are conserved, those metals not found in ash must have escaped in emissions. In a study by Stephens et al. (1972), metal losses (mass entering minus mass in ash) from biosolids incineration ranged from 10 to 640 g Cd day-1, 64 to 499 g Cr day-1, 0 to 290 g Cu day-1, 54 to 64 g Ni day-1, 54 to 145 g Pb day-1, and 163 to 3,541 g Zn day-1. However, pollution abatement equipment was not described, and from the age of the study it can be assumed that the equipment was less effective at that time than it is today. Bennett and Knapp (1982) found that several elements (selenium [Se], vanadium [V], Cu, Zn, Cd, tin [Sn], and Pb) were at higher concentrations in the particles emitted from four incinerators compared to their concentrations in the biosolids feed. This enrichment is attributed to the volatility of the elements and their association with extremely fine particles that are not efficiently removed by scrubbers. A second study by Bennett et al. (1984) found that the ratios of elements in emissions differed considerably from their ratios in biosolids, apparently due to the volatility of some elements, notably Cd, Pb, and Zn. The elements with the largest enrichment ratios (percent in emissions divided by percent in biosolids) were: Cd (31), Zn (14), Pb (9), and sulfur (8). Because of their vapor pressures, Cr, Ni, Cu, Zn, or Pb should not be emitted during pyrolysis when the temperature is less than 750˚ C. However, metals with lower vapor pressures, such as Cd and Hg, can be emitted during pyrolysis or incineration (Kistler et al., 1987). The volume of unfiltered/unscrubbed particulate emissions varies from 4 to 110 mg kg-1 dry biosolids input, depending on the incinerator type and the biosolids composition (Dewling, 1980). Bennett and Knapp (1982) found that particles emitted from three multiplehearth and one fluidized-bed incinerator had small average mass median diameters, ranging from 0.28 to 1.1 µm, with a few larger than 2.0 µm; small particle size promotes dispersion. Particles smaller than 10 µm in diameter are respirable and easily inhaled (Denison and Silbergeld, 1988). In addition, higher concentrations of some metals are often found on small particles, due to the larger surface area to mass ratio of small particles. Bostian et al. (1988) observed that metal emissions are primarily associated with finer particles and noted that this association was likely due to the greater surface area per unit volume (or mass) available for adsorption or condensation on the smaller particles. This characteristic was demonstrated by leaching experiments, in which the increased surface area of finer particles and the presence of metals at or near the surface of such particles exposed to leaching mediums resulted in greater release of metals (Denison and Silbergeld, 1988). In experiments with a pilot-scale multiple-hearth incinerator, between 2 and 11 percent of the feed silver (Ag), Cr, Cu, iron 8 NBMA Summary—Incineration (Fe), Mn, and Ni were found on particulate emissions (Nichols Engineering and Research Corporation, 1981). The combustion temperature during incineration affects metal emissions. The range of combustion temperature is limited on the low end by the need to eliminate odorous matter in the flue gas, and on the high end by the melting temperature of the ash. Therefore, the combustion temperature is usually maintained between 700 and 1,000˚ C (Takeda and Hiraoka, 1976). Importantly, the combustion temperature and the volatility of the metal are the critical factors in determining the amount of the metal emitted from the incinerator. Although high temperature incineration destroys organic compounds, these high temperatures increase the potential for greater metals emission rates (Gerstle and Albrinck, 1982). Emissions of Specific Metals Arsenic. There is limited data available on the fate of As during biosolids combustion. However, As is an element of concern because it is a known human and animal carcinogen as well as a neurotoxin (Denison, 1988). Gerstle and Albrinck (1982) believed As and its compounds should be considered volatile because they may be emitted in larger amounts with increased combustion temperature. As can form the volatile oxide As2O3 (Novak et al., 1977). However, Bostian et al. (1988) did not find that temperature affected enrichment of As in emissions. In mass balance studies, 26 percent of the As in the feed biosolids was lost to stack gas, but it was not discharged to the atmosphere. Campbell et al. (1982) found that As in the scrubber water accounted for all As lost to stack gas, indicating that As associates with larger particles. Cadmium. Because of its low vapor pressure, Cd must be considered a volatile metal (Gerstle and Albrinck, 1982). Kistler (1987) studied biosolids pyrolysis and found that at 505˚ C Cd was retained in the ash; at 750˚ C it was essentially transferred to the off-gas. At 625˚ C, the percent of Cd in the gas or ash depended primarily on the residence time. When the residence time was increased from 1 to 4 hours, the Cd remaining in the ash decreased from 52 percent to 18 percent. Kistler (1987) concluded that “during the pyrolysis of biosolids at T>600˚ C the transfer of Cd to the off-gas cannot be prevented.” He illustrated the mechanisms causing this transfer using Cd carbonate as an example: CdCO3 —> T >400˚ C —> CdO + CO2 CdO + Cchar —> T>625˚ C—> Cd(1) + CO Cd(1) —> T> 625˚ C —> Cd (g) The CdCO3 in the feed biosolids is decomposed to the oxide form and then reduced to the metal. Thus, Kistler attributed the emission of Cd at temperatures exceeding 600˚ C to physiochemical factors and not process design. In pyrolysis experiments conducted by Stammbach et al. (1988), Cd emissions started below 600˚ C and were promoted by small particle size and high turbulence in the fluidizedbed incinerator. 9 NBMA Summary—Incineration Takeda and Hiraoka (1976) observed Cd to be readily vaporized at 450˚ C, with a residual ratio (the amount remaining in the ash to that in the biosolids feed) of 80 percent at 450˚ C and 25 percent at 800˚ C. The authors reported that since most Cd is not caught by the pollution abatement equipment, it is lost in emissions. The enrichment of Cd in emissions was highest at an incinerator with a wet single-pass scrubber system. In the scrubber inlet of this incinerator, 72 percent of the Cd was associated with particles less than 1 µm in diameter (Bennett and Knapp, 1982). Cd emissions increased from 1.0 to 8.1 mg g-1 when incinerator temperature increased from 650 to 950˚ C (Dewling, 1980). Campbell et al. (1982) also stressed that Cd volatilization was a function of temperature with the loss of Cd from fly ash ranging from 25 percent at 760˚ C to 56 percent at 928˚ C in their studies. Bostian et al. (1988) also found Cd enrichment but at insignificant levels. Chromium. The potential for Cr to become volatile during biosolids combustion is low. In Gerstle and Albrinck’s literature review (1982), the authors indicated that less than 1 percent of the Cr in the feed biosolids is associated with fine particles or fume. Tests by Takeda and Hiraoka (1976) showed that over 80 percent of Cr was maintained in ash. Bostian et al. (1988) did not find temperature to have an impact on Cr enrichment in emissions. The oxidation of Cr(III) to Cr(VI) does not occur in pyrolysis but it does in incineration (Majima et al., 1977). However, analytical procedures can yield artificially high concentrations of Cr(IV); sampling of hexavalent Cr without artifact formation and analysis of the resulting samples (specifically for hexavalent Cr at low concentrations) was accomplished by Segall et al. (1992). Copper. Cu is considered to be nonvolatile at incineration temperatures. Takeda and Hiraoka (1976) found that Cu vaporized very little up to 600˚ C; at 800˚ C the residual ratio remained about 85 percent. Lead. Pb is an element of concern because it is neurotoxic at very low concentrations and incremental doses (Denison and Silbergeld, 1988). Although Pb is considered to be nonvolatile, Pb chloride is much more volatile than elemental Pb or Pb oxide. During cooling, Pb oxide is also known to quickly condense on particles (Gerstle and Albrinck, 1982). Pb emissions increased from 3.1 to 77 mg g-1 when incinerator temperature was increased from 650 to 950˚ C, and Pb was associated with particles under 3 µm in diameter (Dewling, 1980). Bostian et al. (1988) reported that Pb enrichment increased with increasing temperatures. EPA research supports this finding (Dewling, 1980). Manganese. Takeda and Hiraoka (1976) found that Mn did not vaporize between 450 and 500˚ C. The residual ratio was about 80 percent at 600˚ C and about 75 percent at 800˚ C. Mercury. Hg is the most volatile of the metals of concern in biosolids (Gerstle and Albrinck, 1982; Kistler, 1987). Hg is neurotoxic and is thought to be particularly damaging to fetal development (Denison, 1988). Hg has a high vapor pressure of 0.16 Pa at 20˚ C, accounting for a saturation concentration of 14 mg of Hg m-3 of air (Kistler et al., 1987). Campbell et al. (1982) found that more than 99 percent of the Hg in the feed stream was emitted from a multiple-hearth incinerator. The proportion of Hg recovered in the scrubber 10 NBMA Summary—Incineration was not determined. Greenberg et al. (1981) found that Hg was emitted in larger quantities than any other toxic compound tested from a Laurel, MD, biosolids incinerator. In a New Jersey fluidized-bed incinerator, approximately 98 percent of the Hg in the feed biosolids was emitted to the atmosphere when combustion temperatures averaged 788˚ C. The study found that only 0.4 percent was retained in the ash, and slightly more than 2 percent was found in the scrubber water (Dewling et al., 1980). In experiments of pyrolysis at 700 and 900˚ C, and incineration at 900˚ C, less than 1 percent of the Hg could be accounted for in the ash (Nichols Engineering and Research Corporation, 1981). Kistler (1987) found that, at varying pyrolysis temperatures (350˚ C, 505˚ C, 625˚ C, and 750˚ C), more than 97 percent of the Hg was emitted. Nickel. Not much is known about the fate of Ni during incineration. Although elemental Ni is nonvolatile, some Ni salts tend to become volatile at incineration temperatures (Gerstle and Albrinck, 1982). Bostian et al. (1988) found no evidence that temperature affects enrichment of Ni in emissions. Segall et al. (1992) found that, within the detection limit of a wet chemical method, no nickel subsulfide was present in emissions. Silver. Few investigations have looked at the fate of Ag during incineration or pyrolysis. However, one experiment found that 60 percent of the Ag was retained in the ash after incineration, while only 20 percent was retained in the ash after pyrolysis. Retention seemed to be unaffected by combustion temperatures of 700 or 900˚ C (Nichols Engineering and Research Corporation, 1981). Zinc. The vapor pressure of Zn indicates that it can be volatile at combustion temperatures (Gerstle and Albrinck, 1982). Takeda and Hiraoka (1976) found that Zn vaporized slightly between 450 and 500˚ C. The residual ratio decreased to 70 percent at 600˚ C and to 60 percent at 800˚ C. However, only 28 percent of the Zn was associated with particles less than 1 µm in diameter (Bennett and Knapp, 1982). Organics and Complete Combustion Hydrophobic hazardous organic compounds (for example, certain pesticides, polynuclear aromatic hydrocarbons, and polychlorinated biphenyls) have been shown to partition onto biosolids during the wastewater treatment process. While control of acid gases (HCl and SO2), trace metals, and particles depends on pollution abatement equipment, control of CO, NOx, and organics is achieved through furnace design and operation. For instance, furnaces designed and operated to achieve nearly complete combustion have low CO emissions (Dewling, 1980). Odors are caused by the formation of partially oxidized hydrocarbons (Dewling, 1980). Wastewater odors, such as those caused by the breakdown of proteins to amines during anaerobic digestion, are eliminated by incineration (Liao and Pilat, 1972). However, more stable organic compounds associated with biosolids are more difficult to destroy completely. Volatile organic emissions are generally much lower from fluidized-bed incinerators than from multiple-hearth incinerators. Emissions of some volatile compounds appear to be 11 NBMA Summary—Incineration products of incomplete combustion (Bostian et al., 1988). Takeda and Hiraoka (1976) also reported that pyrolysis can produce some hydrocarbons, as well as sulfur oxides and nitrogen oxides. In pyrolysis experiments, the amount of gas formed increased with increasing temperatures (Stammbach et al., 1988). Kaminsky and Kummer (1989) reported pyrolysis experiments in which the gaseous portion of the pyrolysis products increased with rising temperature from 22.7 percent at 620˚ C to 40.8 percent at 750˚ C. The pyrolysis gas was analyzed and found to contain hydrogen, methane, ethane, ethene, propene, carbon monoxide, carbon dioxide, and small amounts of other gases including C1–C4 hydrocarbons. In other studies, the amount of ash and gaseous products derived from pyrolysis depended on the temperature and heating rate (Kistler et al., 1987). Principal Organic Hazardous Constituents. Mazer et al. (1987) investigated the potential emissions of organic compounds during biosolids incineration. Thermal decomposition experiments were conducted on biosolids spiked with mixtures of hazardous organic compounds, on the mixtures of pure compounds in the absence of biosolids, and on unspiked biosolids. The findings of this study suggested that the thermal decomposition behavior of principal organic hazardous constituents (POHCs) differed when these compounds were incinerated as mixtures in a biosolids matrix compared to mixtures of pure compounds. The biosolids did not have an effect on the incinerability of easily destructed POHCs. The biosolids appeared to decrease the incinerability of POHCs of intermediate thermal stability (most of the compounds tested), making these POHCs more stable in biosolids. The biosolids increased the incinerability of very stable POHCs, making them more readily destroyed in the presence of biosolids. However, the authors also concluded that interactions between the biosolids and POHCs, such as chlorinated contaminants, may also pose additional health risks in incineration of biosolids from industrial sites. Polychlorinated Dibenzo–p–dioxins and Dibenzofurans. Polychlorinated dibenzo–p–dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are products of combustion. Evidence from sediment cores suggests that PCDDs and PCDFs have significantly increased since 1940, which may be related to increased organohalide production in the United States. PCDDs and PCDFs were first found in the fly ash and flue gas of municipal incinerators in 1977 (Fries and Pausenbach, 1990). The formation of PCDDs and PCDFs from combustion depends on feedstock composition, combustion facility design, and operational parameters such as temperature and air supply. PCDDs and PCDFs were commonly found in incineration fly ash and emissions but only found in trace amounts in a coal-fired power plant. In a study performed by Chiu et al. (1983), all PCDDs and most PCDFs were associated with particles; PCDFs with low molecular weight were found in impingers and XAD (Amberlite XAD–2) adsorbers. (Amberlite XAD–2 is a chemical compound that can be utilized in the measurement of PCDDs and PCDFs through extraction techniques.) Clement et al. (1987) investigated the emissions of chlorinated organics from a 12-hearth incinerator. They found that chlorinated dibenzo–p–dioxins and dibenzofurans were formed during incineration, although at lower concentrations than in municipal incinerators. Incinerators tested by Jones et al. (1987 in Fries and Pausenbach, 1990) emitted from 0.12 to 12 NBMA Summary—Incineration 9.23 ng m-3 (mean 1.75 ng m-3) PCDDs and PCDFs under the standard temperature and pressure . Testing for PCDDs, PCDFs, and 2,3,7,8,–TCDD was performed on 33 municipal incinerators and 17 final disposal sites. Variations in the quantities found depended upon the type of incinerator and operating conditions at the plants (Hiraoka et al., 1987). The results are summarized in Table 1. TABLE 1. PCDDs, PCDFs, and 2,3,7,8,–TCDD Test Results of Municipal Incinerators and Final Disposal Sites (Hiraoka et al., 1987) Incinerator Refuse PCDDs PCDFs TCDDs Fly ash 2.7–10,700 ng g-1 (average 1.0–1,510 ng g-1 523) (average 150) ND–14.5 ng g-1 (average 523) (2,3,7,8,–TCDD ND–4.7 ng g-1) Bottom ash 5.0–2,470 ng g-1 (average 216) 2.3–864 ng g-1 (average 81.9) 0.3–7.3 ng g-1 (average 1.6) (2,3,7,8,–TCDD ND–0.050 ng g-1) Exhaust gas 133–13,600 ng m-3N, (average 510) 436–10,000 ng m-3N (average 2,520) ND–109 ng m-3N (average 54.9) (2,3,7,8,– TCDD ND) Discharged wastewater ND–46.7 ng L-1 ND–285 ng L-1 ND–9.7 ng L-1 Discharged water ND–143 ng L-1 ND–384 ng L-1 ND–11.5 ng L-1 (2,3,7,8,– TCDD ND) Leachate ND–34.0 ng L-1 ND–210 ng L-1 ND–13.7 ng L-1 Ground water ND–8.6 ng L-1 ND–3.9 ng L-1 ND Surface soil 3.2–84.6 ng g-1 (average 22.4) 1.1–447 ng g-1 (average 76.4) ND–1.8 ng g-1 (average 1.3) Final Disposal Site Edgerton (1989) found that municipal solid waste and biosolids incinerators were major potential sources of ambient air concentrations of PCDDs and PCDFs. However, given current knowledge of the health impacts of PCDDs and PCDFs, the low ambient air concentrations were thought to pose no appreciable risk to public health. Concentrations of TCDD in soil are determined by accumulation, mixing, persistence of the compound, and uptake (Fries and Pausenbach, 1990). TCDD remains near the surface on untilled pasture, but is mixed to 15 cm in cropland. TCDD is least persistent (stays in the soil for the least amount of time) when applied in a solution or as vapor to the soil surface and is not incorporated (di Domenico et al., 1982 in Fries and Pausenbach, 1990). TCDD neither leaches nor becomes volatile (Jackson et al., 1985 in Fries and Pausenbach, 1990). Plant uptake of TCDD is negligible. Experiments that found concentrations in plants were probably finding volatilization and redeposition (Fries and Pausenbach, 1990). Little is 13 NBMA Summary—Incineration known about how TCDD impacts fruits and vegetables. The highest interception factors are for leafy vegetables (Baes et al., 1984 in Fries and Pausenbach, 1990), with lettuce and tomatoes having the highest concentration in consumer products. The bulk of TCDD can be removed by washing. For example, for carrots, 97 percent of TCDD was removed by washing and peeling—68 percent by washing alone. Since 80 to 90 percent of roots and tubers are peeled before consumption, the health impact of ingesting these plants was less than expected from the whole vegetable analysis (Pennington, 1983 in Fries and Pausenbach, 1990). Exposure of animals to TCDD from incineration varies with the type of feed (Fries and Pausenbach, 1990). Animals feeding on roughage (for example, hay) can be exposed to TCDD, while animals feeding on concentrates (high energy feed, typically seed) are less likely to be exposed. Seeds are generally protected from direct deposition. Poultry is generally free of TCDD because seeds are protected and the birds are physically protected in houses (North, 1984 in Fries and Pausenbach 1990). Polycyclic Aromatic Hydrocarbons. Concentration of polycyclic aromatic hydrocarbons (PAHs) depends on combustion conditions; more complete combustion forms fewer PAHs. Halogenated hydrocarbons in incineration emissions were below detection limits (Knudson, 1986). Air pollution from continuously operating incinerators with complete combustion is far less than from batch-type incinerators (Kamiya and Ose, 1987a). This is related to poor control over operating conditions during startup and shutdown. For instance, during a 4-hour normal operation of an incinerator, PAHs did not become volatile or decompose (Kamiya and Ose, 1987b). Kamiya and Ose (1987a and 1987b) found that benzo[a]pyrene discharged in emission gas and fly ash was nine times higher from the spray tower than in wastewater. Mutagens in emission gas from complete combustion processes were 10 percent of that for incomplete combustion processes. Ten percent of the mutagens in incinerator’s emission gas was removed by spray tower water and treated as effluent (Kamiya and Ose, 1987b). Both studies by Kamiya and Ose confirmed that there were more mutagens in emission gas than in fly ash and bottom ash. Saxena and Schwartz (1979 in Kamina and Ose, 1987b) argued that wastewater treatment methods were unable to adequately remove potentially hazardous substances; and Shinohara et al. (1980 in Kamina and Ose, 1987b) found that aeration caused PAHs with less than three fused rings to became volatile after 10 hours while those with more than four fused rings decomposed very slowly. The work of Kamiya and Ose (1987b) found results similar to that of Shinohara et al.; specifically, they stated, “...PAHs in wastewater cannot be decomposed by activated sludge using normal aeration times (4 to 5 h).” Polychlorinated Biphenyls. Polychlorinated biphenyls (PCBs) in the atmosphere over the United States are estimated conservatively at 18,000 kg. The source of PCBs to the atmosphere has not been determined. However, landfills and municipal waste incinerators are possible, untested sources. Multiple-hearth incinerators are designed to allow the volatile and evaporative compounds to exit the hearth before combustion. These compounds are then captured in air pollution abatement equipment or exit through the stack (Murphy et al., 1985). 14 NBMA Summary—Incineration Incinerator emissions of PCBs are estimated by Murphy et al. (1985) to average 0.23 kg yr1/stack. This amount of PCBs is minor compared to the total amount of PCBs in the atmosphere above the United States. Dispersion of Emissions Studies on the dispersion of emissions were more prevalent for municipal incinerators than for biosolids incinerators. Thus, a few observations are noted here. Greenberg et al. (1981) compared the relative emissions from a biosolids incinerator with those of other large sources, such as coal-fired plants, municipal incinerators, and Pb from motor vehicles. The authors concluded that, on a per capita basis, the emissions from the incinerator were very small compared to other sources. However, the authors noted that, because the incinerator stack was short, the temperature of the stack emissions was not far above the ambient temperature, and since there were homes within a few hundred meters of the incinerator, the impact of the emissions may have been much greater on the nearby area than in the cases of other sources with greater total emissions but taller stacks. Thus, residents living near a biosolids incinerator could receive considerably greater exposure than in areas impacted by emissions from a coal-fired plant (Greenberg et al., 1981). Berlincioni and di Domenico (1987) tested the emissions of tetra- to octachlorinated PCDDs and PCDFs and resulting soil contamination from a municipal solid waste incinerator in Florence, Italy. Most topsoil sampling sites in the study area were within 1 km of the incinerator. The maximum PCDD soil content found was 7 x 104 ng m-2 of the soil surface. The more chlorinated congeners generally exhibited levels remarkably higher than the less chlorinated ones. Accumulation on plants is related to plant biomass, density, leaf area, roughness, and other factors (Baes et al., 1984), with decreased retention on the plants as the particle size increases (Fries and Pausenbach, 1990). Incinerators with high exhaust temperatures have more volatile 2,3,7,8,–TCDD in vapor form; however, the TCDD is less likely to deposit on soil and plants because it is degraded by ultraviolet radiation (Fries and Pausenbach, 1990). Kukkonen and Raunemaa (1984) investigated the dispersion of emissions from a municipal solid waste incinerator. Out of 17 elements studied, they found the concentrations of 11 elements on birch leaves varied strongly as a function of distance from the incinerator. However, elemental concentrations on grass samples contained more fluctuations and the distance dependency was less clear. In another study (Stephens et al., 1972), foliage of trees in the vicinity of two biosolids incinerators was examined. In the trees with the higher emissions, Pb was always present, although its concentration varied with distance and direction from the incinerator and the highway. Although loss of other metals through emissions exceeded the loss of Pb, only traces of these metals could be found on the foliage; the cause of this phenomenon was unknown. Pollution abatement equipment was not described in this study. However, it can be 15 NBMA Summary—Incineration assumed by the age of the study that the equipment was less effective at the time of the study than it is currently. INCINERATOR ASH Incineration yields odorless, sterile bottom ash and fly ash, which have a combined weight of 10 percent to 60 percent of the original dewatered biosolids cake (Fraser and Lum, 1983; Furr et al., 1979; Denison et al., 1987). Ash typically contains concentrations of trace metals that are four times those in dried biosolids; some of the metals may be at concentrations above 1 percent of the mass of ash (Dewling, 1980). The composition of ash is not well documented. Variations in design, pollution abatement equipment, and operating conditions affect ash characteristics. The cost of disposing incinerator ash is high. Landfilling in sanitary landfills cost from $1.00 to $38.00 per 0.907 mg (with an average cost of $12.79) in 1987 (Repa, 1987). With the closing of many landfills, these costs are increasing dramatically. Other ash disposal practices are more expensive but are often required by state and possibly federal regulations. Nineteen states regulate ash disposal and three require special handling (Governmental Advisory Associates Inc., 1986, in Repa, 1987). Trace Metals in Ash Levels of trace metals in ash can be highly variable. Combustion systems and air pollution control equipment affect the chemical form of metals in bottom ash and fly ash. No correlation was found between extractable and total metals in ash (Wiles, 1988). A study by Sawell et al., (1988) of two Canadian energy-from-waste facilities, which differed in design and pollution abatement equipment, found that concentrations of Cd, Cu, Pb, and Zn were low to moderate in bottom ash. They found that boiler and fly ash samples contained high trace metal concentrations. Bierman et al. (1994) found that concentrations of Cu and Zn in plant tissue were consistently higher and Mn was consistently lower when incinerator ash was used as a fertilizer than when phosphate (P) fertilizer was used. Ash also significantly increased tissue Cd and molybdenum (Mo) in sweet corn. However, trace metal concentrations in tissue were not in the range that would suggest phytotoxicity or animal health problems. Some research has tested the feasibility of metal recovery. Two methods of minimizing trace metals in biosolids and ash are to remove metals from the source or to recover them from the biosolids or ash. Oliver and Carey (1976) investigated recovering metals from ash by using H2SO4 or HCl as an acid extraction procedure to lower the pH to 1.5 and then using vacuum filtration to separate the ash from the leachate. The ash was then disposed of on agricultural land. Results showed that, on average, 50 to 80 percent of the Cd, Cr, Ni, and Zn leached, while the Cu and Pb did not. Over 75 percent of the P, 30 percent of the N, and 10 to 15 percent of the organic carbon also leached. Oliver and Carey attempted a second approach, using H2SO4 or HCl as an acid extraction procedure and then using a two-stage neutralization to precipitate the metals. Results showed that P, Cd, Cr, Ni, and Zn were recoverable, but 66 percent of the Fe leached, which made recovery of P and trace metals more difficult. In an 16 NBMA Summary—Incineration attempt to alleviate this problem, a NH4OH–(NH4)2SO4 method used in ore processing was used to recover the metals; this proved unsuccessful. Oliver and Carey concluded that the acid extraction procedure was prohibitively expensive and separation of metals from ash was more economically feasible for large operations. Organics in Ash Dioxins and other organics associate with the small respirable particles in gas emissions. However, levels of all organics tested were very low in the biosolids incinerator bottom ash examined by Clement et al. (1987). Polychlorinated Dibenzo–p–dioxins and Dibenzofurans. Organic compounds created during combustion include dioxins and furans. Total dioxins in municipal solid waste incineration ash ranged from 20 to 20,000 ppb, with 0.1 to 8 ppb of 2,3,7,8,–TCDD (Denison et al., 1987). TABLE 2. Concentrations of Total and Leachable Toxic Metals in Municipal Solid Waste Incinerator Ash in the United States (Wiles, 1988) Compound Bottom Ash (mg kg-1) Bottom Ash Leachate (mg L-1) Fly Ash (mg kg-1) Fly Ash Leachate (mg L-1) Pb 31 to 36,600 0.02 to 34 2 to 26,600 0.019 to 53.35 Cd 0.18 to 100 0.018 to 3.94 5 to 2,210 0.025 to 100 As 0.8 to 50 ND(0.001) to .0122 4.8 to 750 ND(0.001 to 0.858) Cr 13 to 1,500 ND(0.007) to 0.46 21 to 1,900 0.006 to 0.135 Barium (Ba) 47 to 2000 0.27 to 6.3 88 to 9000 0.67 to 22.8 Ni ND(1.5) to 12,91 0.241 to 2.03 ND(1.5) to 3,600 0.09 to 2.90 Cu 40 to 10,700 0.039 to 1.19 187 to 2,300 0.033 to 10.6 ( ) = below detection limits The bioavailability of dioxins in fly ash is inversely related to the organic carbon content of the ash. Therefore, better combustion and stack controls may yield ash with a greater dioxin exposure. Bioaccumulation of PCDDs and PCDFs from municipal solid waste incinerator fly ash in Carp (Cyprinus carpio) was tested by Kuehl et al. (1987). Previous studies showed a strong preference for 2,3,7,8,–TCDD bioaccumulation, but the concentration was not directly related to the concentration in the original incinerator fly ash. Ingestion of fly ash from sediments was thought to be the primary route of carp exposure. Preferential accumulation occurred for compounds with chlorine in the 2,3,7, and 8 positions. The Bioavailability Index (contaminant in fish to contaminant in fly ash) decreased with increasing chlorination (Kuehl et al., 1987). Polycyclic Aromatic Hydrocarbons. Wszolek (1982) investigated the presence of PAHs in incinerated biosolids ash. PAHs are known to be a product of combustion, and some PAHs are carcinogenic and mutagenic. PAHs and other trace organics have been found in the fly 17 NBMA Summary—Incineration ash from incinerated municipal solid waste. Wszolek found a wide range in the amount (0.1 to 1.0 µg g-1) and variety of PAHs. No clear correlation was found between the amount of PAHs and the industrial input into the wastewater of the cities studied. Polychlorinated Biphenyls. Few studies have investigated the presence of PCBs in incinerated biosolids ash. However, Furr et al. (1979) reported finding no PCBs in incinerated biosolids ash of 10 cities in the United States. This is possibly due to thermal decomposition or condensates that have become volatile on escaping particulates. Comparison of the Impact of Pyrolysis and Incineration on Ash Content The type of plant and pollution abatement equipment affects the characteristics of the ash. This review focuses on the differences between pyrolysis and incineration. Pyrolysis. In pyrolysis experiments, Kaminsky and Kummer (1989) found that trace metals were more strongly incorporated into the matrix of pyrolysis ash than in incinerated ash or biosolids. They found that 70 percent of the Cd, 100 percent of the Cr, 95 percent of the Cu, 87 percent of the Ni, 92 percent of the Pb, and 89 percent of the Zn that were present in the feed biosolids remained in pyrolysis ash. The authors concluded that, with the exception of the volatile metals (Hg and Cd), trace metals originating from the biosolids were enriched in pyrolysis ash. For Cd, the pyrolysis temperature and residence time were significant, while Hg was already volatile at temperatures below 500˚ C. Kistler et al. (1987) studied both raw and digested biosolids and found that Cr, Ni, Cu, Zn, and Pb were completely retained in pyrolysis ash up to the maximum investigated temperature of 750˚ C. The studies classified the metals as follows: • Cr, Ni, Cu, Zn, and Pb are nonvolatile under pyrolysis conditions up to 705˚ C • Cd is volatile under pyrolysis conditions at temperatures exceeding 600˚ C • Hg is volatile under pyrolysis conditions at temperatures exceeding 350˚ C The studies also found that the amount of metals leached from pyrolysis ash was very small, with concentrations low enough to be better than drinking water standards. The authors concluded that the high H+ buffering capacity and the alkaline nature of the slaked chars rendered the metals in the char very immobile. Thus, the pyrolysis char appeared to be suitable for disposal in a sanitary landfill. However, since these metals might be mobilized by a combination of acids and organic liquids, they should be disposed of in landfills where organic material is excluded (“monofill”). The results of pyrolysis experiments in a multiple-hearth incinerator indicate that lowering furnace temperature from 900 to 700˚ C improves metal retention in the ash from 50 percent to 90 percent for Be, from 10 to 30 percent to 50 percent for Cd, and from 30 to 50 percent to 60 percent for Pb (Nichols Engineering and Research Corporation, 1981). 18 NBMA Summary—Incineration Incineration. It is important to note that incineration and pyrolysis can yield different emissions and ash quality. Few studies have examined this issue, although one study found that incineration retained 60 percent of the feed Ag in the ash, whereas pyrolysis retained only 20 percent. Cr, Cu, Fe, Mn, Ni, and Zn were entirely retained in the ash regardless of the mode of operation (Nichols Engineering and Research Corporation, 1981). Dewling et al. (1980) described the distribution of trace metals in a fluidized-bed biosolids incinerator. The percent of each metal studied found in the ash, scrubber water, and stack emissions are shown in Table 3. TABLE 3. Normalized Distribution of Trace Metals at a FluidizedBed Incinerator (Percent of Weight) Compound Ash Scrubber Stack Emissions Zn 79.0 20.0 1.0 Cu 78.0 21.0 1.0 Pb 87.0 12.0 1.0 Cr 95.0 4.0 1.0 Ni 80.0 20.0 ND Hg 0.4 2.0 97.6 Cd 80.0 20.0 ND ND = below detection limits Leachate Liquids (water or other weak solvents) passed through ash will extract soluble and weakly held metal ions and other dissolvable compounds. This is often used as a method to assess the availability of a particular contaminant to plants or animals, or the potential of the contaminant to pass through the soil into the groundwater. Availability of metals in leachate decreases with increasing incinerator temperature (Oliver and Carey, 1976), which makes it difficult to compare different studies. A study of ash from incinerated New Jersey municipal solid waste found that Cd and Pb leached from the fly ash in excessive concentrations (15 to 18 ppm for Cd, 27 to 44 ppm for Pb), creating a serious disposal problem. Furthermore, this problem was magnified by increases in acid concentrations of the leaching medium (Clapp et al., 1988). di Casa et al. (1982) also found excessive leaching of Cd, Cu, Ni, and Pb from ash from a municipal incinerator in northern Italy and suggested this ash was the source of groundwater contamination. Behel et al. (1986) investigated various amendments to reduce the solubility of Cd and Pb in incinerator ash. Pb solubility was reduced by amendments of CaO, CaCO3, acidic NH4H2PO4, basic K2HPO4, and elemental Se. Cd solubility was reduced by CaO and the P 19 NBMA Summary—Incineration amendments. Malone and Jones (1985) also investigated three stabilization treatments and found that the addition of lime to fly ash to form a cement-like solid proved to be the most durable treatment and reduced leaching to the greatest extent. However, none of the treated products were very durable. In leaching studies with soil amended with fly and bottom ash from municipal incinerators, it was found that Cd, and, to a lesser extent Pb, were much more mobile than if similar concentrations of these elements had been applied as inorganic salts or in biosolids (Giordano, 1983). Repa (1987), using the EP toxicity test, also found high concentrations of Pb and Cd in leachate. All other metals were below regulatory limits, and all organics tested were below regulatory limits. Fraser and Lum (1983) investigated the availability of elements in incinerated biosolids ash and found that above 90 percent of the Cd, Cr, Cu, Ni, Pb, and Zn were in unavailable forms. The measurable, but small, amounts of aluminum (Al), Cr, Mn, Ni, Pb, and P present in the ash could be released, however, if the ash were to come into contact with ice or snow melt contaminated with road salt or acid rain. Only a small fraction of metals were recovered in leachate by Klei et al. (1981); cobalt (Co), Pb, and Fe were undetectable. It was suggested that acid conditions of at a pH of 4.0 would have increased leaching two- to threefold. It is believed that calcium (Ca) and Cr could be recovered from incinerator ash. A study of incinerated biosolids ash found that, once initial leaching of trace metals occurred, leaching rates were very slow. Fe was found to leach in the highest concentration of the metals studied, with leaching loss of more than 4 percent (by weight) of the initial Fe in the ash. Other metals leached the following percentages of their initial concentrations in the ash: Ca (2.30 percent), Mg (1.10 percent), and K (0.95 percent). Zn, sodium (Na), Mn, Cr, Co, Pb, and Ni leached less than 0.20 percent (Sweeney, 1978). Theis and Padgett (1983) looked at extractable trace metals from biosolids incinerator ash and dewatered biosolids using the EP toxicity test. The test was based on a 5 percent ash in a 95 percent municipal solid waste landfill in which decomposition of municipal solid waste produces acids. Repa (1987) found that ash used as a daily cover or mixed with municipal solid waste is most likely to encounter acid leaching, while monofills are least likely. Theis and Padgett (1983) found that elevated concentrations of Fe, Al, and Ca were common for locations using FeCl2, AlSO4, or lime to condition biosolids, which affected EP toxicity test results. Incineration of biosolids increased the leachability of all metals except Cd, and As if Fe(III) or Al(III) salts were added. Sequential extraction (a series of leachings on the same sample with different strength solvents) indicated that Cd and Pb were associated with the amorphous Al oxides, and Fe, Cr, and Ni were associated with Fe oxyhydroxides. There was little correlation between the amount of element released and the amount of the element in bulk ash or biosolids. Maskarinec et al. (1987) investigated laboratory extraction procedures for testing leachate. In the study, lysimeters packed with municipal solid waste were treated with distilled water to generate a municipal waste leachate. This leachate was then used to leach a variety of industrial wastes, including resource recovery ash (the result of processes 20 NBMA Summary—Incineration producing “energy-from-waste”), a biosolids incinerator ash mixture, and a coking plant wastewater treatment sludge (the result of coal combustion processes). The resulting leachates were analyzed for both inorganic and organic constituents. Inorganic constituents showed two distinct types of leaching behavior: freely soluble elements (for example, B, Na, and Ca) had leaching curves that showed exponential decline; acid-soluble elements (Ni and Zn) eluded as “peaks” as the pH of the leachate decreased. Organic constituents gave leaching curves that were dependent on solubility: either an exponential decline (freely soluble compounds) or a relatively flat curve at or near the solubility limit. Because of the possibility of acid leachate in municipal landfills, monofills are considered to be a more appropriate means of disposal. Two studies considered the reactions that may occur in monofills. Hjelmar (1988) tested bottom and fly ash from two Danish municipal solid waste incinerators not equipped with scrubbers with a column leaching test. Solid residue from municipal solid waste incinerators is typically 80 to 90 percent bottom ash and 10 to 20 percent fly ash. For most metals, increased leaching corresponded to increased fly ash content of the mixture tested. Concentrations of metals leached in the column leaching test were higher than concentrations in leachate from the incinerator ash monofill that had been monitored for 15 years by landfill operators. The only exceptions were for SO42- and Ca2+; these were highly saturated in the accelerated column experiments. Similarly, Krebs et al. (1988) explored the main reaction of bottom ash with water, the long-term mobilization potential of indicator elements from ash, and the feasibility of bottom ash monofills as a means of long-term storage. Solutions were analyzed for Ca, Na, potassium (K), Al, OH-, Cl-, SO42-, P, NO3-, NH4+, COD, Zn, Pb, Cd, and Cu. Ca2+, Na+, K+, and Cl- increased in solution with increasing reaction time with bottom ash. OH- decreased in concentration after 50 hours of reaction time, while other elements stayed constant or increased slowly. OH-, Cl-, and Al(OH)4- dissolution occurred before dissolution of SO42-. During the first decade after disposal, leaching should occur under alkaline conditions, with total organic carbon as a main variable in the long-term behavior of bottom ash. Health Effects Exposure to dust, surface soils, reentrained particles, contaminated food, and drinking water all constitute postdepositional exposure. The importance of postdepositional exposure can be seen in major studies of Pb exposure, which indicate postdepositional exposure to Pb is 5 to 50 times more intense than ambient air exposure. Other exposure pathways involve ash handling and disposal, including: 1) handling, storage, transport, and disposal of ash and other waste products of incineration; 2) exposure to airborne dust, suspended particles, and contaminated soil from landfills; 3) direct ground and surface water contamination by leachate; 4) erosion of landfill cap; and 5) transport of metals out of the landfill by plant uptake and burrowing animals (Denison and Silbergeld, 1988; Denison et al., 1987). In addition, workers in biosolids incinerators can be exposed to airborne irritants. Nethercott (1981) investigated an outbreak of dermatitis among workers at a biosolids incinerator. The outbreak was caused when the workers replaced a malfunctioning incinerator exhaust fan and were exposed to airborne irritants. The problems ceased when skin contact with the irritants was minimized. 21 NBMA Summary—Incineration Stern et al. (1989) assessed the potential exposure levels and pursuant public health implications of neighborhood exposure to a landfill which, from 1954 to 1973, received bottom ash from a municipal incinerator. The incinerator processed residential and commercial waste, but not industrial waste. Soil was sampled for 10 trace metals, PCDDs, PCDFs, 2–3–7–8–TCDD and TCDF congeners, PCBs, and PAHs. The results of soil analysis and modeling indicated that the Pb level at the landfill was considerably above the level recommended by the Center for Disease Control and could lead to Pb poisoning in exposed children. The health impact of exposure to other substances measured in the soil was considered to be small, and no significant increased cancer risk was expected. It is important to note that the incinerator that supplied the ash used no air pollution control devices to collect fly ash, whereas most modern incinerators do. Fly ash and bottom ash are now routinely co-disposed. Because the landfill received no fly ash, results from this study are not necessarily applicable to disposal sites containing both fly and bottom ash. Trace Metals. Trace metals exert a broad range of toxic effects, including carcinogenic, neurological, hepatic, renal, hematopoietic, and other adverse effects (Denison and Silbergeld, 1988). Metal emissions can have direct inhalation effects or secondary and tertiary effects after fallout (Dewling, 1980). Trace metals accumulate in the environment and in the human body. Pb is neurotoxic at very low doses, and prenatal neurological effects occur at any level of Pb exposure. With Pb exposure already a problem from automobile emissions, paint, and other sources, even small increases in Pb exposure can drastically increase the incidence of Pb toxicity. Cd is also neurotoxic and can damage the lung and kidneys. It is carcinogenic and may be toxic to fetuses. Pb and Cd may act synergistically as toxins to bone. Hg is neurotoxic in organic forms, and microorganisms in the environment can alkylate inorganic Hg into hazardous organic forms. As is neurotoxic and carcinogenic. Hg, As, Cd, Zn, and Cu are toxic to aquatic organisms. For an extensive review of the toxicology of trace metals see Friberg et al. (1986). In addition, a comprehensive list of metallic carcinogens, designated by the International Agency for Research on Cancer, appears as Appendix A in Knudson (1986). Polychlorinated Dibenzo–p–dioxins and Dibenzofurans. Potential sources for human exposure to TCDD in food is now believed to stem more from combustion and waste disposal practices than phenoxy herbicide production (Fries and Pausenbach, 1990). TCDD is not genotoxic (EPA, 1988a in Fries and Pausenbach, 1990); its half-life in human adipose tissue is 7 years (Poiger and Schlatter, 1986 in Fries and Pausenbach, 1990; Pirkle et al., 1989 in Fries and Pausenbach, 1990). Incinerators located in rural areas can potentially contaminate milk, meat, and vegetables with TCDD (Fries and Pausenbach, 1990). A population near the incinerator source can potentially receive 500 to 1,000 times greater exposure to TCDD from food than from inhalation. Using models of radioactive deposition, dispersion, and bioaccumulation, Fries and Pausenbach (1990) reviewed TCDD bioaccumulation and routes of exposure, then estimated TCDD deposition and transfer to the food chain from incinerators. The review found that soil 22 NBMA Summary—Incineration accumulation was less important than direct plant deposition and the forage–cattle–beef pathway was more important than the forage–dairy cow–milk pathway in human exposure. Animal food sources contained an estimated 10 to 40 fg kg-1 d-1 and plant food sources contained an estimated 1 to 5 fg kg-1 d-1. Fries and Pausenbach concluded that exposure from incinerators was insignificant compared to background sources. The concentration of PCDDs and PCDFs in human milk samples is a possible route of infant exposure. The possible risk from municipal solid waste incinerator emissions was analyzed based on formulas presented by Fries and Pausenbach (1990). The maximum levels of PCDDs and PCDFs from incinerators would account for 1 to 10 percent of the PCDD and PCDF levels in milk; other sources of PCDDs and PCDFs must account for the additional PCDD and PCDF found in milk (Smith, 1987). The toxicity and toxic potential of fly ash can affect aquatic life. Helder et al. (1982) assessed the impact of fly ash on rainbow trout yolk sac fry. Fry exposed to fly ash showed no toxic response during the 60-day test, but fry exposed to raw extract (using toluene) and cleaned extract (passed through a column of silica gel and acid-, base-, and silver nitratemodified silica gel) became inactive, stopped feeding, hemorrhaged, and finally died from severe edema. Toxic response was similar to toxic response for 2,3,7,8,–TCDD, but only minor quantities of 2,3,7,8,–TCDD were found in extracts. Response was attributed to a combined effect of TCDDs and TCDFs. Incineration of biosolids produces dioxins and is thought to make the highest contribution to the general background. However, Fiedler and Hutzinger (1992) estimated that, besides combustion processes, nonthermal waste treatment methods, such as composting, represent a reservoir to the release of PCDDs and PCDFs in agriculture. Polycyclic Aromatic Hydrocarbons. Gustavsson (1989) investigated mortality for workers at a municipal incinerator in Stockholm, Sweden. Workers were exposed to PAHs, other polycyclic compounds, dust, nitrous oxides, sulfur dioxide, carbon monoxide, and several trace metals. The incinerator used in this study was an older incinerator that caused more environmental contamination and occupational exposure than modern plants. The study found that lung cancer risk was 3.5 times higher than the national rate, and 2 times higher than the local rate. Although eight out of nine lung cancer deaths were attributed to smokers, the rate increase could not be attributed solely to smoking. Metal exposure was thought to be too low to cause lung cancer. Additionally, ischemic heart disease was higher than expected by national and local standards. The association between PAH and lung cancer is well documented, but the association of ischemic heart disease is not. Gustavsson (1989) further suggested that exposure to PAHs, TCDDs, and TCDFs may relate to increased atherosclerosis, but precise evidence is lacking. Uses of Incinerated Ash The expense of landfilling incinerator ash has led to research into alternate uses of incinerated biosolids ash. Ash has been studied as a soil amendment, although there may be problems with trace metal concentrations. Another option for highly contaminated ash has 23 NBMA Summary—Incineration been to use it as a cement filler, which would stabilize the hazardous constituents. Finally, some form of solidification into a usable product may be possible. Soil Amendment. Biosolids ash may be used as a soil amendment, particularly as it often contains several essential macro- and micro-nutrients. Fitzpatrick (1985) investigated the use of biosolids ash as a growing media for containerized tropical trees. He found that four of the five species studied grew equally well in this media compared to a traditional growing media. Rosen (1989) studied the use of biosolids incinerator ash as a source of P for the production of corn. For early growth, at equivalent P rates, corn response was greater for the fertilizer treatment than for the ash treatment. However, final yield was unaffected by treatment. In comparing the fertilizer properties of biosolids and its incinerated ash, Jakobsen and Willett (1986) found that biosolids were a better fertilizer. Although biosolids and ash were both good sources of lime and, in the short-term, ash was more effective in raising soil pH, the biosolids were more effective in raising extractable P. The biosolids were also a good source of nitrogen (N) and P, and increased foliar concentrations of K, Se, Mg, Cu, and Zn. The ash was not a source of N or P, and increased only Se and Mg. The ash also appeared to decrease the availability of K, Cu, and Zn. Some characteristics of incinerated ash can be detrimental to plant growth. Eis (1978) studied revegetation problems at a landfill that contained ash from incinerated municipal solid waste. Revegetation had low success because of the ash characteristics, which included high porosity, low water-holding capacity, very low N and P content, and toxic concentrations of Se, Zn, and Pb. Although incinerated biosolids ash may sometimes be used as a soil amendment, Mellbye (1982) noted that its use on agricultural land may be limited by the concentration and availability of trace metals in the ash. Plant uptake and phytotoxicity vary considerably between inorganic and organic sources of elements; thus, information from studies on metal availability from soils amended with biosolids may not be wholly applicable to soil amended with incinerated biosolids ash. In experiments by Giordano et al. (1983), corn and Swiss chard were grown in greenhouse pots of Decatur silt loam amended with fertilizer as well as 300 g of fly ash or 600 g of bottom ash. The chard displayed a positive growth response to both ash treatments. The plants were tested for concentrations of Cd, Pb, Zn, Ni, Na, and Mn. Na, Cd, Pb, and possibly Mn were found at levels considered to be excessive. In experiments with corn, Rosen (1989) found ash to be a good source of Zn, which can be limited at high rates of P. However, Zn was found to move through the soil profile. Other trace metals such as Cd, Pb, Ni, and Cr did not move out of the top 15.24 cm, nor did they accumulate in the corn grain, stover, or cob. Bierman and Rosen (1994) evaluated biosolids incinerator ash as a P fertilizer on corn grown in an Estherville sandy loam (sandy, mixed, mesic Typic Hapludol). Limited effects on growth occurred the first 2 years, and significant increases in yield occurred in the third 24 NBMA Summary—Incineration and fourth years. The ash increased Cu, Cd, Mo, P, and Zn concentrations in plant tissue. However, the increase did not reach phytotoxicity levels. Furr et al. (1979) investigated the absorption of elements by cabbage growing on soil amended with incinerated biosolids ash. One objective of the study was to determine if the cabbage would absorb elements in proportion to their concentrations in the ash. Although Ni and Zn were found in high concentrations in the ash, absorption by the cabbage was low, possibly because these elements were present in the ash in insoluble compounds formed during incineration. Fe, Mn, and Pb were higher in the control cabbage than in any of the cabbage grown in the ash. These elements may have been present naturally in the soil but were unavailable in the ash. Cement Filler. Tay (1987) found that that biosolids ash could be used as a partial replacement for cement. Lisk (1989) also investigated this use of biosolids ash and found that some mixtures created a cement that met the specifications for compressive strength for masonry cement. Lisk also found that the strength of the cement generally decreased with increasing percentages of bottom ash; fly ash (which is more homogeneous and finer than bottom ash) became more intimately mixed with cement particles, thus creating a stronger product. Solidification. In Japan, the use of incinerated biosolids ash as brick has been practiced as an alternative to disposal (NEDO, 1994). Solidification of ash is possible, but results in a 5 to 50 percent volume increase, and the reagent materials may be prohibitively expensive. However, these costs may be acceptable if the ash is classified as a hazardous waste. Another option is to screen ash and dispose of larger, nontoxic particles as nonhazardous material while solidifying the smaller particles; this might reduce costs as well as prevent leaching. If solidified material is used for building materials, exposure to biota may represent a hazard. Studies of breakwater concrete and attached marine life indicated no metal uptake, although these results were preliminary (Wiles, 1988). SUMMARY Biosolids incineration is practiced in the United States and remains a viable biosolids management alternative. However, incineration yields both emissions and ash. Potential environmental impacts of and concerns regarding incineration include: 1) air pollution from emissions; 2) water pollution from boiler blowdown and scrubber water discharge; 3) decreased effluent quality from recirculating loads; and 4) ash handling and disposal. Additionally, deposition onto the soil from emissions can gradually degrade soil quality. Thus, regulations have been developed to minimize the risk to humans and the environment. Modern incinerators are increasingly equipped with pollution abatement equipment, but such devices increase the amount of ash and change its nature. Emissions Emissions from incinerators include particulates, water vapor, heat, CO, CO2, SO2, NOx, hydrocarbons, volatile organics, and metals. Of the metals, Hg is the most volatile; As, Cd, 25 NBMA Summary—Incineration and Zn are considered to be at least partially volatile; Pb and Ni are not volatile except in salt form, and Cu and Cr are generally retained in the ash. Toxic organics can also be found in emissions, either originating from the feedstock (for example, PCBs and PAHs), or as a result of the incineration process (for example, dioxins and dibenzofurans). Emission or production of these organics is, again, dependent upon feedstock and operation. Ash Biosolids incineration yields an odorless, sterile ash, which typically contains trace metals concentrations that are four times those in dried biosolids. Levels of trace metals in ash can be highly variable. The combustion system and air pollution control equipment affects the chemical form of metals in bottom ash and fly ash. In contrast, of the organics tested, concentrations are usually very low in biosolids incinerator bottom ash. Leachate from ash can be contaminated with soluble metals. Generally, availability of metals in the leachate decreases with increasing incinerator temperature. However, acidic conditions in leachate will increase concentrations of the metals. Thus, because of the possibility of acid leachate in municipal landfills, monofills are considered to be more appropriate means of disposal. The expense of landfilling incineration ash has led to research into alternate uses of incinerated biosolids ash. Ash contains both macro- and trace nutrients, can be used as a liming material to raise soil pH, and studies have investigated its use as a soil amendment. However, plant uptake and phytotoxicity vary considerably between ash types. Studies have also investigated the use of ash as a cement filler and as a building material (when solidified). Health Effects Exposure to dust, surface soils, reentrained particles, contaminated food, and drinking water all constitute postdepositional exposure; postdepositional exposure may be 5 to 50 times more intense than ambient air exposure. Other pathways of exposure involve ash handling and disposal, including: 1) handling, storage, transport, and disposal of ash and other waste products of incineration, 2) exposure to airborne dust, suspended particles, and contaminated soil from landfills, 3) direct ground and surface water contamination by leachate, 4) erosion of landfill cap, and 5) transport of metals out of the landfill by plant uptake and burrowing animals. The incineration of biosolids are known to produce dioxins and are thought to make the highest contribution to the general background. Reference: Henry, C., and R. Harrison. 1998. Environmental Effects of Biosolids Management. Trace Metals: Potential for Movement and Toxicity from Biosolids Application, Effects on Wildlife and Domestic Animals from Biosolids Application, Air Emissions and Ash Resulting from Incineration of Biosolids, Nitrogen Cycle and Nitrate Leaching from Biosolids Application, Microbial Activity, Survival and Transport in Soils Amended with Biosolids, The Fate of Trace Synthetic Organics in Biosolids Applied to Soil, Runoff Water Quality from Biosolids Application, Effects of Organic Residuals on Poplars. Northwest Biosolids Management Association. 26