REMEDIATION OF PETROLEUM CONTAMINATED SOILS - SECTION 3 ppsx

Section 3 Biodegradation/Mineralization/Biotransformation/ Bioaccumulation of Petroleum Constituents and Associated Heavy Metals 3.1 CHEMICAL COMPOSITION OF FUEL OILS 3.1.1 NAPHTHA 3.1.2 KEROSENE 3.1.3 FUEL OIL AND DIESEL #2 Table 3.1 lists organic compounds found in diesel fuel #2, as reported by Clewell, 1981. 3.1.4 GASOLINE Tables 3.2 through 3.4 list the organic compounds and trace elements found in gasoline, as reported by different references. 3.1.5 JP-5 Tables 3.5 through 3.7 list the organic compounds and trace elements found in JP-5, as reported by different references. 3.1.6 JP-4 Tables 3.8 through 3.10 list the organic compounds and trace elements found in JP-4, as reported by different references. 3.2 ORGANIC COMPOUNDS Crude oil is a highly complex mixture, containing hundreds of thousands of hydrocarbons (Cooney, 1980). Compounds in crude oil can be divided into three general classes consisting of saturated hydro- carbons, aromatic hydrocarbons, and polar organic compounds (Huesemann and Moore, 1993). Saturated hydrocarbons can be separated further into straight-chain and branched alkanes, as well as cyclic alkanes with varying numbers of saturated rings and side chains. Aromatic hydrocarbons contain one or more aromatic rings ranging from simple monoaromatic compounds, such as benzene and toluene to polyar- omatic compounds, such as pyrene. The polar fraction is made of compounds containing “polar” heteroatoms, such as nitrogen, sulfur, and oxygen. Refined oils are also complex; for example, kerosene may contain as many as 10,000 different hydrocarbons (Sharpley, 1964). This complexity also extends to other petroleum products (Atlas, 1977). For microorganisms to biodegrade petroleum completely or attack even simpler refined oils, thousands of different compounds must be metabolized. The chemical nature of these petroleum components varies from the simple n -paraffin, monoalicyclic, and monoaromatic compounds, to the much more complex branched chains and condensed ring structures (Horowitz, Sexstone, and Atlas, 1978). Many different enzymes are presumably necessary to biodegrade these types of compounds. The principal biochemical reactions associated with the microbial metabolism of xenobiotics include acylation, alkylation, dealkylation, dehalogenation, amide or ester hydrolysis, oxidation, reduction, aromatic ring hydroxylation, ring cleavage, and condensate or conjugate formation (Kaufman and Plimmer, 1972). Microbial action is initiated at metal, sulfur, and other functional group sites, and proceeds to breakage of carbon–carbon bonds, even to biocracking of heavy petroleums (Premuzic, Lin, Racaniello, and Manowitz, 1993). Subsurface screening of petroleum hydrocarbons in contaminated soils can be conducted with laser- induced fluorometry over optical fibers with a cone penetrometer system to identify the contaminants as an initial step in the remediation process (Lieberman, Apitz, Borbridge, and Theriault, 1993). The © 1998 by CRC Press LLC system provides the capability for real-time, in situ measurement of petroleum hydrocarbon contamina- tion and soil type to depths of 50 m. A common technique for measuring the biodegradability of an organic compound is calculation of the BOD/COD ratio. This ratio is an indication of the amount of degradation that occurs, or biochemical oxygen demand (BOD), relative to the amount of material available to be degraded, chemical oxygen Table 3.1 Composition of Diesel Fuel #2 Concentration Concentration Component (% Volume) Component (% Volume) C 10 paraffins 0.9 C 15 paraffins 7.4 C 10 cycloparaffins 0.6 C 15 cycloparaffins 5.5 C 10 aromatics 0.4 C 15 aromatics 3.2 C 11 paraffins 2.3 C 16 paraffins 5.8 C 11 cycloparaffins 1.7 C 16 cycloparaffins 4.4 C 11 aromatics 1.0 C 16 aromatics 2.5 C 12 paraffins 3.8 C 17 paraffins 5.5 C 12 cycloparaffins 2.8 C 17 cycloparaffins 4.1 C 12 aromatics 1.6 C 17 aromatics 2.4 C 13 paraffins 6.4 C 18 paraffins 4.3 C 13 cycloparaffins 4.8 C 18 cycloparaffins 3.2 C 13 aromatics 2.8 C 18 aromatics 1.8 C 14 paraffins 8.8 C 19 paraffins 0.7 C 14 cycloparaffins 6.6 C 19 cycloparaffins 0.6 C 14 aromatics 3.8 C 19 aromatics 0.3 Source: From Clewell, H.J., III. The Effect of Fuel Composition on Groundfall from Aircraft Fuel Jettisoning. Report. Air Force Engineering and Services Center, Tyndall Air Force Base, FL, 1981. Table 3.2 Composition of Various Gasolines Paraffins Propane Dimethyl pentanes Isobutane (1C 4 ) Methyl hexanes n -Butane (nC 4 ) Trimethyl pentanes Isopentane (1C 5 ) Normal heptane n -Pentane (1C 5 ) Dimethyl hexanes Dimethyl butanes (C 6 ) Methylethyl pentanes Methyl pentanes (C 6 ) Dimethyl hexanes n -Hexane Trimethyl hexanes n -Octane Naphthenes Methylcyclopentane Methylcyclohexane Cyclohexane Other cyclic saturates Aromatics Benzene Propylbenzene Toluene Methylethylbenzenes Ethylbenzene Trimethylbenzene Xylenes Other aromatics Olefins Methylbutene Methylpentene Pentene Other olefins Source: From Ghassemi, M. et al. Energ. Sourc. 7:377–401, 1984. With permission. © 1998 by CRC Press LLC demand (COD). Table 3.11 presents relative biodegradabilities by adapted sludge cultures of various substances in terms of a BOD/COD ratio, after 5 days of incubation (U.S. EPA, 1985a). A higher ratio represents a higher relative biodegradability. As the ratio approaches zero, the compound becomes less degradable. Recalcitrant compounds are more difficult to treat with microorganisms. Nevertheless, there are microbes and techniques available for dealing with such contaminants. For example, a novel Pseudomo- nas anaerooleophila , which is resistant to aliphatic, alicyclic, and aromatic carbohydrates, or a mixture thereof, has been patented by Imanaka and Morikawa (1993). This strain, HD-1, can grow in a medium containing n- tetradecane, toluene, cyclohexane, and petroleum and can be useful for treating environ- mental pollutants. Novotny (1992) has even characterized some thermophilic microorganisms that can utilize recalcitrant substrates. Many different types of microorganisms are involved in biodegradation. These range from microbes that require oxygen to perform the catabolic reactions to those that require an anaerobic environment. Table 3.12 summarizes several microbial processes and shows an approximate relationship between the process and the environmental redox potential (Berry, Francis, and Bollag, 1987). The more negative the number, the stronger the reducing environment, as can be seen by the strict requirement for anaerobiosis. A database has been developed to provide rapid, reliable information on the biodegradability of soil pollutants and on possible bioremedial action (Gleim, Milch, and Kracht, 1995). The database was created to facilitate better transfer of scientific results on biodegradation of soil pollutants to those involved in bioremedial action. Information in the database is derived from international scientific publications on biodegradation. It includes information on polycyclic aromatic hydrocarbons (PAHs), Table 3.3 Components of Gasoline Component Component n -Propane 3,3-Dimethylpentane n -Butane 2,3-Dimethylpentane n -Pentane 2,5-Dimethylhexane n -Hexane 2,4-Dimethylhexane n -Heptane 2,3-Dimethylhexane n -Octane 3,4-Dimethylhexane n-cis -Butene-2 2,2-Dimethylhexane n -Pentane-2 2,2-Dimethylheptane 2,3-Dimethylbutene-1 1,1-Dimethylcyclopentane Olefins C 4 1,2- and 1,3-Dimethylcyclopentane Olefins C 5 1,3- and 1,4-Dimethylcyclohexane Olefins C 6 1,2-Dimethylcyclohexane Isobutane 2,2,3-Trimethylbutane Cyclopentane 2,2,4-Trimethylpentane Cyclohexane 2,2,3-Trimethylpentane Methylcyclopentane 2,3,4-Trimethylpentane Methylcyclohexane 2,3,3-Trimethylpentane 2-Methylbutane 2,2,5-Trimethylpentane 2-Methylpentane 1,2,4-Trimethylcyclopentane 3-Methylpentane Ethylpentane 2-Methylhexane Ethylcyclopentane 3-Methylhexane Ethylcyclohexane 2-Methylheptane Benzene 3-Methylheptane Ethylbenzene 4-Methylheptane Toluene 2,2-Dimethylbutane o -Xylene 2,3-Dimethylbutane m -Xylene 2,2-Dimethylpentane p -Xylene 2,4-Dimethylpentane Source: From Jamison, V.W. et al. in Proc. 3rd Int. Biodegradation Symp. Sharpley, J.M. and Kaplan, A.M., Eds. Elsevier, New York. 1976. With permission. © 1998 by CRC Press LLC Table 3.4 Composition of Gasoline Number of Concentration Compound Carbons (w%) Straight Chain Alkanes Propane 3 0.01 to 0.14 n -Butane 4 3.93 to 4.70 n -Pentane 5 5.75 to 10.92 n -Hexane 6 0.24 to 3.50 n -Heptane 7 0.31 to 1.96 n -Octane 8 0.36 to 1.43 n -Nonane 9 0.07 to 0.83 n -Decane 10 0.04 to 0.50 n -Undecane 11 0.05 to 0.22 n -Dodecane 12 0.04 to 0.09 Branched Alkanes Isobutane 4 0.12 to 0.37 2,2-Dimethylbutane 6 0.17 to 0.84 2,3-Dimethylbutane 6 0.59 to 1.55 2,2,3-Trimethylbutane 7 0.01 to 0.04 Neopentane 5 0.02 to 0.05 Isopentane 5 6.07 to 10.17 2-Methylpentane 6 2.91 to 3.85 3-Methylpentane 6 2.4 (vol) 2,4-Dimethylpentane 7 0.23 to 1.71 2,3-Dimethylpentane 7 0.32 to 4.17 3,3-Dimethylpentane 7 0.02 to 0.03 2,2,3-Trimethylpentane 8 0.09 to 0.23 2,2,4-Trimethylpentane 8 0.32 to 4.58 2,3,3-Trimethylpentane 8 0.05 to 2.28 2,3,4-Trimethylpentane 8 0.11 to 2.80 2,4-Dimethyl-3-ethylpentane 9 0.03 to 0.07 2-Methylhexane 7 0.36 to 1.48 3-Methylhexane 7 0.30 to 1.77 2,4-Dimethylhexane 8 0.34 to 0.82 2,5-Dimethylhexane 8 0.24 to 0.52 3,4-Dimethylhexane 8 0.16 to 0.37 3-Ethylhexane 8 0.01 2-Methyl-3-ethylhexane 9 0.04 to 0.13 2,2,4-Trimethylhexane 9 0.11 to 0.18 2,2,5-Trimethylhexane 9 0.17 to 5.89 2,3,3-Trimethylhexane 9 0.05 to 0.12 2,3,5-Trimethylhexane 9 0.05 to 1.09 2,4,4-Trimethylhexane 9 0.02 to 0.16 2-Methylheptane 8 0.48 to 1.05 3-Methylheptane 8 0.63 to 1.54 4-Methylheptane 8 0.22 to 0.52 2,2-Dimethylheptane 9 0.01 to 0.08 2,3-Dimethylheptane 9 0.13 to 0.51 2,6-Dimethylheptane 9 0.07 to 0.23 3,3-Dimethylheptane 9 0.01 to 0.08 3,4-Dimethylheptane 9 0.07 to 0.33 2,2,4-Trimethylheptane 10 0.12 to 1.70 3,3,5-Trimethylheptane 10 0.02 to 0.06 3-Ethylheptane 10 0.02 to 0.16 2-Methyloctane 9 0.14 to 0.62 3-Methyloctane 9 0.34 to 0.85 © 1998 by CRC Press LLC 4-Methyloctane 9 0.11 to 0.55 2,6-Dimethyloctane 10 0.06 to 0.12 2-Methylnonane 10 0.06 to 0.41 3-Methylnonane 10 0.06 to 0.32 4-Methylnonane 10 0.04 to 0.26 Cycloalkanes Cyclopentane 5 0.19 to 0.58 Methylcyclopentane 6 Not quantified 1-Methyl- cis -2-ethylcyclopentane 8 0.06 to 0.11 1-Methyl- trans -3-ethylcyclopentane 8 0.06 to 0.12 1- cis -2-Dimethylcyclopentane 7 0.07 to 0.13 1- trans -2-Dimethylcyclopentane 7 0.06 to 0.20 1,1,2-Trimethylcyclopentane 8 0.06 to 0.11 1- trans -2- cis -3-Trimethylcyclopentane 8 0.01 to 0.25 1- trans -2- cis -4-Trimethylcyclopentane 8 0.03 to 0.16 Ethylcyclopentane 7 0.14 to 0.21 n -Propylcyclopentane 8 0.01 to 0.06 Isopropylcyclopentane 8 0.01 to 0.02 1- trans -3-dimethylcyclohexane 8 0.05 to 0.12 Ethylcyclohexane 8 0.17 to 0.42 Straight Chain Alkenes cis -2-Butene 4 0.13 to 0.17 trans -2-Butene 4 0.16 to 0.20 Pentene-1 5 0.33 to 0.45 cis -2-Pentene 5 0.43 to 0.67 trans -2-Pentene 5 0.52 to 0.90 cis -2-Hexene 6 0.15 to 0.24 trans -2-Hexene 6 0.18 to 0.36 cis -3-Hexene 6 0.11 to 0.13 trans -3-Hexene 6 0.12 to 0.15 cis -3-Heptene 7 0.14 to 0.17 trans -2-Heptene 7 0.06 to 0.10 Branched Alkenes 2-Methyl-1-butene 5 0.22 to 0.66 3-Methyl-1-butene 5 0.08 to 0.12 2-Methyl-2-butene 5 0.96 to 1.28 2,3-Dimethyl-1-butene 6 0.08 to 0.10 2-Methyl-1-pentene 6 0.20 to 0.22 2,3-Dimethyl-1-pentene 7 0.01 to 0.02 2,4-Dimethyl-1-pentene 7 0.02 to 0.03 4,4-Dimethyl-1-pentene 7 0.6 (vol) 2-Methyl-2-pentene 6 0.27 to 0.32 3-Methyl- cis -2-pentene 6 0.35 to 0.45 3-Methyl- trans -2-pentene 6 0.32 to 0.44 4-Methyl- cis -2-pentene 6 0.04 to 0.05 4-Methyl- trans -2-pentene 6 0.08 to 0.30 4,4-Dimethyl- cis -2-pentene 7 0.02 4,4-Dimethyl- trans -2-pentene 7 Not quantified 3-Ethyl-2-pentene 7 0.03 to 0.04 Table 3.4 (continued) Composition of Gasoline Number of Concentration Compound Carbons (w%) © 1998 by CRC Press LLC Cycloalkenes Cyclopentene 5 0.12 to 0.18 3-Methylcyclopentene 6 0.03 to 0.08 Cyclohexene 6 0.03 Alkyl Benzenes Benzene 6 0.12 to 3.50 Toluene 7 2.73 to 21.80 o -Xylene 8 0.68 to 2.86 m -Xylene 8 1.77 to 3.87 p -Xylene 8 0.77 to 1.58 1-Methyl-4-ethylbenzene 9 0.18 to 1.00 1-Methyl-2-ethylbenzene 9 0.19 to 0.56 1-Methyl-3-ethylbenzene 9 0.31 to 2.86 1-Methyl-2- n -propylbenzene 10 0.01 to 0.17 1-Methyl-3- n -propylbenzene 10 0.08 to 0.56 1-Methyl-3-isopropylbenzene 10 0.01 to 0.12 1-Methyl-3- t -butylbenzene 11 0.03 to 0.11 1-Methyl-4- t -butylbenzene 11 0.04 to 0.13 1,2-Dimethyl-3-ethylbenzene 10 0.02 to 0.19 1,2-Dimethyl-4-ethylbenzene 10 0.50 to 0.73 1,3-Dimethyl-2-ethylbenzene 10 0.21 to 0.59 1,3-Dimethyl-4-ethylbenzene 10 0.03 to 0.44 1,3-Dimethyl-5-ethylbenzene 10 0.11 to 0.42 1,3-Dimethyl-5- t -butylbenzene 12 0.02 to 0.16 1,4-Dimethyl-2-ethylbenzene 10 0.05 to 0.36 1,2,3-Trimethylbenzene 9 0.21 to 0.48 1,2,4-Trimethylbenzene 9 0.66 to 3.30 1,3,5-Trimethylbenzene 9 0.13 to 1.15 1,2,3,4-Tetramethylbenzene 10 0.02 to 0.19 1,2,3,5-Tetramethylbenzene 10 0.14 to 1.06 1,2,4,5-Tetramethylbenzene 10 0.05 to 0.67 Ethylbenzene 8 0.36 to 2.86 1,2-Diethylbenzene 10 0.57 1,3-Diethylbenzene 10 0.05 to 0.38 n -Propylbenzene 9 0.08 to 0.72 Isopropylbenzene 9 <0.01 to 0.23 n -Butylbenzene 10 0.04 to 0.44 Isobutylbenzene 10 0.01 to 0.08 sec-Butylbenzene 10 0.01 to 0.13 t -Butylbenzene 10 0.12 n -Pentylbenzene 11 0.01 to 0.14 Isopentylbenzene 11 0.07 to 0.17 Indan 9 0.25 to 0.34 1-Methylindan 10 0.04 to 0.17 2-Methylindan 10 0.02 to 0.10 4-Methylindan 10 0.01 to 0.16 5-Methylindan 10 0.09 to 0.30 Tetralin 10 0.01 to 0.14 Polynuclear Aromatic Hydrocarbons Naphthalene 10 0.09 to 0.49 Pyrene 16 Not quantified Table 3.4 (continued) Composition of Gasoline Number of Concentration Compound Carbons (w%) © 1998 by CRC Press LLC Benz(a)anthracene 18 Not quantified Benzo(a)pyrene 20 0.19 to 2.8 mg/kg Benzo(e)pyrene 20 Not quantified Benzo(g,h,i)perylene 21 Not quantified Elements Bromine 80 to 345 µg/g Cadmium 0.01 to 0.07 µg/g Chlorine 80 to 300 µg/g Lead 530 to 1120 µg/g Sodium <0.6 to 1.4 µg/g Sulfur 0.10 to 0.15(ASTM) Vanadium <0.02 to 0.001 µg/g Additives Ethylene dibromide 0.7 to 177.2 ppm Ethylene dichloride 150 to 300 ppm Tetramethyl lead Tetraethyl lead Source: From State of California. Leaking Underground Fuel Tank Field Manual. Aca- demic Press, Orlando, FL, 1987. With permission. Table 3.5 Selected Compound Types Occurring in JP-5 Aromatic Partial Saturation Saturated Benzene — Cyclohexane Indene Indane Hydrindane (Indan) (Hydroindane) Naphthalene Tetralin Decalin (Tetrahydronaphthalene) (Decahydronaphthalene) Acenaphthalene Acenaphthene Perhydroacenaphthalene Phenanthrene Tetrahydrophenanthrene Perhydrophenanthrene Source: From Varga, G.M., Jr. et al. Report to Naval Air Propulsion Center, Contract N00140-81-C-9601, 1985. NAPC-PE-121C. Table 3.6 Trace Elements in Shale-Derived JP-5 Element ppm Element ppm Element ppm Al 0.048 Cu <0.02 Si Ϲ 10 Sb <3 Fe <0.01 Ag <0.02 As <0.5 Pb <0.06 Na 0.14 Be <0.01 Mg <5.3 Sr Ϲ 0.94 Cd <0.02 Mn <0.02 Tl <6 Ca Ϲ 0.6 Hg <2 Sn Ϲ 0.93 Cl <2 Mo Ϲ 0.03 Ti < 0.4 Cr Ϲ 0.094 Ni <3.9 V Ϲ 0.0008 Co Ϲ 0.04 Se <0.5 Zn Ϲ 0.02 Source: Ghassemi, M., Panahloo, A., and Quinlivan, S. Environ. Toxicol. Chem. 3:511–535. Society of Environmental Toxicology and Chemistry (SETAC). 1984. With permission. Table 3.4 (continued) Composition of Gasoline Number of Concentration Compound Carbons (w%) © 1998 by CRC Press LLC halogenated compounds, degradation in soils, and use of pure or mixed cultures. The files cover compounds, mixtures and classes of compounds, microorganisms, culture conditions, metabolism/metab- olites, soil properties, experimental scale and experimental conditions, bioremediation treatment, deg- radation data, and bibliography. The language of the database was German until April 1994, after which Table 3.7 Major Components of JP-5 Concentration Concentration Fuel Component (w%) Fuel Component (w%) n -Octane 0.12 n -Dodecane 3.94 1,3,5-Trimethylcyclohexane 0.09 2,6-Dimethylundecane 2.00 1,1,3-Trimethylcyclohexane 0.05 1,2,4-Triethylbenzene 0.72 m -Xylene 0.13 2-Methylnaphthalene 0.90 3-Methyloctane 0.07 1-Methylnaphthalene 1.44 2,4,6-Trimethylheptane 0.09 1-Tridecene 0.45 o -Xylene 0.09 Phenylcyclohexane 0.82 n -Nonane 0.38 n -Tridecane 3.45 1,2,4-Trimethylbenzene 0.37 1- t -Butyl-3,4,5-trimethylbenzene 0.24 n -Decane 1.79 n -Heptylcyclohexane 0.99 n -Butylcyclohexane 0.90 n -Heptylbenzene 0.27 1,3-Diethylbenzene 0.61 Biphenyl 0.70 1,4-Diethylbenzene 0.77 1-Ethylnaphthalene 0.32 4-Methyldecane 0.78 2,6-Dimethylnaphthalene 1.12 2-Methyldecane 0.61 n -Tetradecane 2.72 1-Ethylpropylbenzene 1.16 2,3-Dimethylnaphthalene 0.46 n -Undecane 3.95 n -Octylbenzene 0.78 2,6-Dimethyldecane 0.72 n -Pentadecane 1.67 1,2,3,4-Tetramethylbenzene 1.48 n -Hexadecane 1.07 Naphthalene 0.57 n -Heptadecane 0.12 2-Methylundecane 1.39 Source: From Smith, J.H. et al. SRI Int., Menlo Park, CA. Report No. ESL-TR-81-54. Engineering and Services Laboratory, Tyndall Air Force Base, FL, 1981. Table 3.8 Composition of JP-4 Concentration Concentration Component (% Volume) Component (% Volume) C 5 hydrocarbons 3.9 C 11 paraffins 4.8 C 6 paraffins 8.1 C 11 cycloparaffins 2.5 C 6 cycloparaffins 2.1 Dicycloparaffins 3.4 Benzene 0.3 C 11 aromatics 1.1 C 7 paraffins 9.4 C 11 naphthalenes 0.2 C 7 cycloparaffins 7.1 C 12 paraffins 2.8 Toluene 0.7 C 12 cycloparaffins 1.2 C 8 paraffins 10.1 C 12 aromatics 0.5 C 8 cycloparaffins 7.4 C 12 naphthalenes 0.2 C 8 aromatics 1.6 C 13 paraffins 1.1 C 9 paraffins 9.1 C 13 cycloparaffins 0.4 C 9 cycloparaffins 4.3 C 13 aromatics 0.1 C 9 aromatics 2.4 C 14 hydrocarbons 0.2 C 10 paraffins 7.3 C 15 hydrocarbons 0.1 C 10 cycloparaffins 3.7 Tricycloparaffins 1.8 C 10 aromatics 1.8 Residual hydrocarbons 0.1 Napthalene 0.2 Source: From Clewell, H.J., III. The Effect of Fuel Composition on Groundfall from Aircraft Fuel Jettisoning, Air Force Engineering and Services Center, Tyndall Air Force Base, FL, 1981. © 1998 by CRC Press LLC it was continued in English. The database was projected to be available in 1996 on diskettes (MS-DOS) from the DSM-Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Germany. 3.2.1 AEROBIC DEGRADATION Some compounds appear to be degraded only under aerobic conditions, others only under anaerobic conditions, and some under either condition, while others are not transformed at all. It has been concluded that hydrocarbons are subject to both aerobic and anaerobic oxidation (Dietz, 1980). The first stage of biodegradation of insoluble hydrocarbons is predominantly aerobic, while the organic carbon content is then reduced by anaerobic action. Table 3.9 Major Components of JP-4 Concentration Concentration Fuel Component (w%) Fuel Component (w%) n-Butane Isobutane n-Pentane 2,2-Dimethylbutane 2-Methylpentane 3-Methylpentane n-Hexane Methylcyclopentane 2,2-Dimethylpentane Benzene Cyclohexane 2-Methylhexane 3-Methylhexane trans-1,3-Dimethylcyclopentane cis-1,3-Dimethylcyclopentane cis-1,2-Dimethylcyclopentane n-Heptane Methylcyclohexane 2,2,3,3-Tetramethylbutane Ethylcyclopentane 2,5-Dimethylhexane 2,4-Dimethylhexane 1,2,4-Trimethylcyclopentane 3,3-Dimethylhexane 1,2,3-Trimethylcyclopentane Toluene 2,2-Dimethylhexane 2-Methylheptane 4-Methylheptane cis-1,3-Dimethylcyclohexane 3-Methylheptane 1-Methyl-3-ethylcyclohexane 1-Methyl-2-ethylcyclohexane Dimethylcyclohexane n-Octane 1,3,5-Trimethylcyclohexane 1,1,3-Trimethylcyclohexane 2,5-Dimethylheptane Ethylbenzene 0.12 0.66 1.06 0.10 1.28 0.89 2.21 1.16 0.25 0.50 1.24 2.35 1.97 0.36 0.34 0.54 3.67 2.27 0.24 0.26 0.37 0.58 0.25 0.26 0.25 1.33 0.71 2.70 0.92 0.42 3.04 0.17 0.39 0.43 3.80 0.99 0.48 0.52 0.37 m-Xylene p-Xylene 3,4-Dimethylheptane 4-Ethylheptane 4-Methyloctane 2-Methyloctane 3-Methyloctane o-Xylene 1-Methyl-4-ethylcyclohexane n-Nonane Isopropylbenzene n-Propylbenzene 1-Methyl-3-ethylbenzene 1-Methyl-4-ethylbenzene 1,3,5-Trimethylbenzene 1-Methyl-2-ethylbenzene 1,2,4-Trimethylbenzene n-Decane n-Butylcyclohexane 1,3-Diethylbenzene 1-Methyl-4-propylbenzene 1,3-Dimethyl-5-ethylbenzene 1-Methyl-2-i-propylbenzene 1,4-Dimethyl-2-ethylbenzene 1,2-Dimethyl-4-ethylbenzene n-Undecane 1,2,3,4-Tetramethylbenzene Naphthalene 2-Methylundecane n-Dodecane 2,6-Dimethylundecane 2-Methylnaphthalene 1-Methylnaphthalene n-Tridecane 2,6-Dimethylnaphthalene n-Tetradecane 0.96 0.35 0.43 0.18 0.86 0.88 0.79 1.01 0.48 2.25 0.30 0.71 0.49 0.43 0.42 0.23 1.01 2.16 0.70 0.46 0.40 0.61 0.29 0.70 0.77 2.32 0.75 0.50 0.64 2.00 0.71 0.56 0.78 1.52 0.25 0.73 Source: From Smith, J.H. et al. SRI Int., Menlo Park, CA. Report No. ESL-TR-81-54. Engineering and Services Laboratory, Tyndale Air Force Base, 1981. © 1998 by CRC Press LLC For most compounds, the most rapid and complete degradation occurs aerobically (U.S. EPA, 1985a). It can be generalized that for the degradation of petroleum hydrocarbons, aromatics, halogenated aro- matics, polyaromatic hydrocarbons, phenols, halophenols, biphenyls, organophosphates, and most pes- ticides and herbicides, aerobic bioreclamation techniques are most suitable. Aerobic degradation with methane gas as the primary substrate appears promising for some low-molecular-weight halogenated hydrocarbons. Microorganisms have evolved catabolic enzyme systems for metabolism of naturally occurring aro- matic compounds (Gibson, 1978). In the oxidation of aromatic hydrocarbons, oxygen is the key to the hydroxylation and fission of the aromatic ring. Bacteria incorporate two atoms of oxygen into the hydrocarbons to form dihydrodiol intermediates. The hydroxyl groups are cis-dihydrodiols. Oxidation of the dihydrodiols leads to the formation of catechols, which are substrates for enzymatic cleavage of the aromatic ring. In contrast, certain strains of fungi and higher organisms (eukaryotes) incorporate one atom of molecular oxygen into aromatic hydrocarbons to form arene oxides, which can undergo the Table 3.10 Trace Elements in Petroleum-Based JP-4 Element ppm Element ppm Element ppm Al NA Cu <0.05 Si NA Sb <0.5 Fe <0.05 Ag NA As 0.5 Pb 0.09 Na NA Be NA Mg NA Sr NA Cd <0.03 Mn NA Th NA Ca NA Hg <1 Sn NA Cl NA Mo NA Ti NA Cr <0.05 Ni <0.05 V <0.05 Co NA Se <0.03 Zn <0.05 NA = not applicable. Source: From Ghassemi, M. et al. Environ. Toxicol. Chem. 3:511–535. Society of Environmental Toxicologicy and Chemistry (SETAC), 1984. With permission. Table 3.11 BOD 5 /COD Ratios for Various Organic Compounds Compound Ratio Compound Ratio Relatively Undegradable Heptane 0 m-Xylene <0.008 Hexane 0. Ethylbenzene <0.009 o-Xylene <0.008 Moderately Degradable Gasolines (various) 0.02 p-Xylene <0.11 Nonanol >0.033 Toluene <0.12 Undecanol <0.04 Jet fuels (various) 0.15 Dodecanol 0.097 Kerosene 0.15 Relatively Degradable Naphthalene (molten) <0.20 Jet fuels (various) 0.15 Hexanol 0.20 Kerosene 0.15 Benzene <0.39 Benzaldehyde 0.62 p-Xylene <0.11 Phenol 0.81 Toluene <0.12 Benzoic acid 0.84 Source: Lyman, W.J. et al. in Handbook of Chemical Properties Estimation Methods: Environmental Behavior of Organic Chemicals, McGraw-Hill, New York, 1982. Chap. 16. Reprinted in U.S. EPA Handbook No. EPA/625/6-85/006, 1985. © 1998 by CRC Press LLC [...]... Methylcyclopentane 2-Methylbutane 2-Methylpentane 3- Methylpentane 3- Methylhexane 2-Methylheptane 3- Methylheptane 2,2-Dimethylbutane 2 , 3- Dimethylbutane 2,2-Dimethylpentane 2,4-Dimethylpentane 2 , 3- Dimethylpentane 2 , 3- Dimethylhexane 1,2-Dimethylcyclohexane 2,2,4-Trimethylpentane (isooctane) 2 ,3, 4-Trimethylpentane (isooctane) 2 ,3, 3-Trimethylpentane (isooctane) Ethylcyclohexane Benzene Ethylbenzene Toluene o-Xylene m-Xylene... 2-Methylpentane 3- Methylpentane 2-Methylhexane 3- Methylhexane 2-Methylheptane 3- Methylheptane 4-Methylheptane 2,2-Dimethylbutane 2 , 3- Dimethylbutane 2,2-Dimethylpentane 2,4-Dimethylpentane 3, 3-Dimethylpentane 2 , 3- Dimethylpentane Percent Biodegraded above Control 0 0 70 46 49 54 0 16 18 0 0 45 10 75 0 6 7 23 0 38 45 48 25 0 9 11 45 0 Component 2,5-Dimethylhexane 2,4-Dimethylhexane 2 , 3- Dimethylhexane 3, 4-Dimethylhexane... 2,2-Dimethylhexane 2,2-Dimethylheptane 1,1-Dimethylcyclopentane 1, 2- and 1 , 3- Dimethylcyclopentane 1, 3- and 1,4-Dimethylcyclohexane 1,2-Dimethylcyclohexane 2,2 , 3- Trimethylbutane 2,2,4-Trimethylpentane 2,2 , 3- Trimethylpentane 2 ,3, 4-Trimethylpentane 2 ,3, 3-Trimethylpentane 2,2,5-Trimethylpentane 1,2,4-Trimethylcyclopentane Ethylpentane Ethylcyclopentane Ethylcyclohexane Benzene Ethylbenzene Toluene o-Xylene... constituents of the gasoline than the individual isolates, suggesting a form of mutualism © 1998 by CRC Press LLC Table 3. 16 Growth of Microorganisms on Components of Gasoline Compound n-Alkanes Cyclic alkanes Alkyl-substituted cyclicalkane Monomethylalkanes Dimethylalkanes Trimethylalkanes Aromatics n-Butane n-Pentane n-Hexane n-Heptane n-Octane n-cis-Butene-2 n-Pentane-2 2 , 3- Dimethylbutene-1 Cyclopentane... 4-hydroxy-1-tetralone, and trans-1,2-dihydroxy-1,2-dihydronaphthalene The primary metabolite is 1-naphthol Cunninghamella bainieri oxidizes naphthalene through trans-1,2-dihydroxy-1,2-dihydronaphthalene (Gibson and Mahadevan, 1975) C elegans oxidizes naphthalene by a sequence of reactions resulting in six metabolites: 1-naphthol, 4-hydroxy-1-tetralone, 1,4-naphthoquinone, 1,2-naphthoquinone, 2-naphthol,... degradation of low-molecular-weight PAHs may also induce that of higher-molecular-weight compounds (Stringfellow, Chen, and Aitken, 1995) For instance, salicylate can induce degradation of phenanthrene, and © 1998 by CRC Press LLC phenanthrene or salicylate can induce metabolism of pyrene and fluoranthene by Pseudomonas saccharophila P-15 While five- and six-ring PAHs are degraded along with two- through four-ring... 2-naphthol, and trans-1,2-dihydroxy-1,2-dihydronaphthalene A Nocardia sp can biotransform naphthalene and substituted naphthalenes to their corresponding diols (Hou, 1982) Naphthalene is oxidized by species of Cunninghamella, Syncephalastrum, and Mucor to 2-naphthol, 4-hydroxy-1-tetralone, trans-naphthalene dihydrodiol, 1,2-naphthoquinone, 1,4-naphthoquinone, and predominantly 1-naphthol (Cerniglia,... days, respectively In general, the four-, five-, and six-ring PAHs have half-lives of over 200 days The half-lives determined under laboratory conditions may be considerably shorter than those in the field (Wild, Berrow, and Jones, 1991) Biodegradation of high-molecular-weight PAHs sorbed to silt and clay particles can be enhanced by the presence of low-molecular-weight PAHs; for example, PAHs with four... on p-xylene in the presence of toluene (Chang, Voice, and Criddle, 19 93) The fungus Phanerochaete chrysosporium can degrade xylenes under nonlignolytic culture conditions in a nitrogen-rich medium (Paszczynski and Crawford, 1995) A Nocardia sp growing on hexadecane converts p-xylene to p-toluic acid and 2 , 3- dihydroxy-p-toluic acid (Ooyama and Foster, 1965) A Nocardia sp co-oxidizes primarily o-xylene... primarily o-xylene and p-xylene; o-xylene is oxidized to o-toluic acid, ethylcyclohexane to cyclohexane acid, p-xylene to p-toluic acid, and 2-methylheptane to a mixture of products, including ketones and aldehydes (Jamison, Raymond, and Hudson, 1976) When two components of gasoline are combined, one for growth and one as a co-oxidizable substrate, a Pseudomonas sp is able to co-oxidize o-xylene with hexane . to 0. 03 4,4-Dimethyl-1-pentene 7 0.6 (vol) 2-Methyl-2-pentene 6 0.27 to 0 .32 3- Methyl- cis -2 -pentene 6 0 .35 to 0.45 3- Methyl- trans -2 -pentene 6 0 .32 to 0.44 4-Methyl- cis -2 -pentene. 0.56 1-Methyl -3 - ethylbenzene 9 0 .31 to 2.86 1-Methyl- 2- n -propylbenzene 10 0.01 to 0.17 1-Methyl- 3- n -propylbenzene 10 0.08 to 0.56 1-Methyl -3 - isopropylbenzene 10 0.01 to 0.12 1-Methyl- 3- . (w%) n-Butane Isobutane n-Pentane 2,2-Dimethylbutane 2-Methylpentane 3- Methylpentane n-Hexane Methylcyclopentane 2,2-Dimethylpentane Benzene Cyclohexane 2-Methylhexane 3- Methylhexane trans-1 , 3- Dimethylcyclopentane cis-1 , 3- Dimethylcyclopentane cis-1,2-Dimethylcyclopentane n-Heptane Methylcyclohexane 2,2 ,3, 3-Tetramethylbutane Ethylcyclopentane 2,5-Dimethylhexane 2,4-Dimethylhexane 1,2,4-Trimethylcyclopentane 3, 3-Dimethylhexane 1,2 , 3- Trimethylcyclopentane Toluene 2,2-Dimethylhexane 2-Methylheptane 4-Methylheptane cis-1 , 3- Dimethylcyclohexane 3- Methylheptane 1-Methyl -3 - ethylcyclohexane 1-Methyl-2-ethylcyclohexane Dimethylcyclohexane n-Octane 1 ,3, 5-Trimethylcyclohexane 1,1 , 3- Trimethylcyclohexane 2,5-Dimethylheptane Ethylbenzene 0.12 0.66 1.06 0.10 1.28 0.89 2.21 1.16 0.25 0.50 1.24 2 .35 1.97 0 .36 0 .34 0.54 3. 67 2.27 0.24 0.26 0 .37 0.58 0.25 0.26 0.25 1 .33 0.71 2.70 0.92 0.42 3. 04 0.17 0 .39 0. 43 3.80 0.99 0.48 0.52 0 .37 m-Xylene p-Xylene 3, 4-Dimethylheptane 4-Ethylheptane 4-Methyloctane 2-Methyloctane 3- Methyloctane o-Xylene 1-Methyl-4-ethylcyclohexane n-Nonane Isopropylbenzene n-Propylbenzene 1-Methyl -3 - ethylbenzene 1-Methyl-4-ethylbenzene 1 ,3, 5-Trimethylbenzene 1-Methyl-2-ethylbenzene 1,2,4-Trimethylbenzene n-Decane n-Butylcyclohexane 1 , 3- Diethylbenzene 1-Methyl-4-propylbenzene 1 , 3- Dimethyl-5-ethylbenzene 1-Methyl-2-i-propylbenzene 1,4-Dimethyl-2-ethylbenzene 1,2-Dimethyl-4-ethylbenzene n-Undecane 1,2 ,3, 4-Tetramethylbenzene Naphthalene 2-Methylundecane n-Dodecane 2,6-Dimethylundecane 2-Methylnaphthalene 1-Methylnaphthalene n-Tridecane 2,6-Dimethylnaphthalene n-Tetradecane 0.96 0 .35 0. 43 0.18 0.86 0.88 0.79 1.01 0.48 2.25 0 .30 0.71 0.49 0. 43 0.42 0. 23 1.01 2.16 0.70 0.46 0.40 0.61 0.29 0.70 0.77 2 .32 0.75 0.50 0.64 2.00 0.71 0.56 0.78 1.52 0.25 0. 73 Source: