Downloaded From : www.EasyEngineering.net Handbook of Environmental Engineering Calculations, 2nd edition by C C Lee, Shun Dar Lin ww w.E asy En gi nee rin g ne t • ISBN: 0071475834 • Pub Date: May 2007 • Publisher: McGraw-Hill Companies Downloaded From : www.EasyEngineering.net Downloaded From : www.EasyEngineering.net Table of Contents Pt Calculations of Water Quality Assessment and Control 01 Basic Science and Fundamentals 02 Streams and Rivers 03 Lakes and Reservoirs 04 Groundwater 05 ww Fundamental and Treatment Plant Hydraulics 06 Public Water Supply Pt Solid Waste Calculations 07 08 09 w.E asy Wastewater Engineering Thermodynamics used in Environmental Engineering En gi Basic Combustion and Incineration 10 Practical Design of Waste Incineration 11 Calculations for Permitting and Compliance 12 nee rin g Calculational Procedures for Ash Stabilization and Solidification 13 Incineration Technologies and Facility Requirements Pt Air Pollution Control Calculations 14 Air Emission Control 15 Particulate Emission Control 16 Wet and Dry Scrubbers for Emission Control 17 Air Toxic Risk Assessment 18 Fundamentals Of Fuel Cell Technologies ne t Downloaded From : www.EasyEngineering.net Source: HANDBOOK OF ENVIRONMENTAL ENGINEERING CALCULATIONS Downloaded From : www.EasyEngineering.net P A ● ● R T ● ● CALCULATIONS OF WATER QUALITY ASSESSMENT AND CONTROL ww w.E asy En gi Part of this book is written for use by the following readers: students taking coursework relating to public water supply, waste-water engineering or stream sanitation, practicing environmental (sanitary) engineers; regulatory officers responsible for the review and approval of engineering project proposals; operators, engineers, and managers of water and/or wastewater treatment plants; and any other professionals, such as chemists and biologists, who have gained some knowledge of water/wastewater issues This work will benefit all operators and managers of public water supply and of wastewater treatment plants, environmental design engineers, military environmental engineers, undergraduate and graduate students, regulatory officers, local public works engineers, lake managers, and environmentalists The chapters in Part present the basic principles and concepts relating to water/wastewater engineering and provide illustrative examples of the subject To the extent possible, examples rely on practical field data Each of the calculations provided herein are solved step-by-step in a streamlined manner that is intended to facilitate understanding Calculations (step-by-step solutions) range from calculations commonly used by operators to more complicated calculations required for research or design Advances and improvements in many fields are driven by competition or the need for increased profits It may be fair to say, however, that advances and improvements in environmental engineering are driven instead by regulation The US Environmental Protection Agency (EPA) sets up maximum contaminant levels, which research and project designs must reach as a goal The step-by-step solution examples provided in this book are informed by the integration of rules and regulations on every aspect of waters and wastewaters The author has performed an extensive survey of literature on surface and groundwaters encountered in environmental engineering and compiled them in the following chapters Rules and regulations are described as simply as possible, and practical examples are given The following chapters include calculations for basic science, surface waters ground water, drinking water treatment, and wastewater engineering Chapter 1.1 covers conversion factors between the two measurement systems, the United States (US) customary system and the System International (SI), basic mathematics for water and wastewater plant operators, fundamental chemistry and physics, and basic statistics for environmental engineers nee rin g ne t Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website CALCULATIONS OF WATER ASSESSMENT AND CONTROL Downloaded FromQUALITY : www.EasyEngineering.net 1.2 PART ww Chapter 1.2 comprises calculations for river and stream waters Stream sanitation had been studied for nearly 100 years By the mid-twentieth century, theoretical and empirical models for assessing waste assimilating capacity of streams were well developed Dissolved oxygen and biochemical oxygen demand in streams and rivers have been comprehensively illustrated in this chapter Apportionment of stream users and pragmatic approaches for stream dissolved oxygen models are also covered From the 1950s through the 1980s, researchers focused extensively on wastewater treatment In 1970s, rotating biological contactors also became a hot subject Design criteria and examples for all of these are included Some treatment and management technologies are no longer suitable in the United States However, they are still of some use in developing countries Chapter 1.3 is a compilation of adopted methods and documented research In the early 1980s, the USEPA published Guidelines for Diagnostic and Feasibility Study of Public Owned Lakes (Clean Lakes Program, or CLP) This was intended to be used as a guideline for lake management CLP and its calculation (evaluation) methods are present in this chapter Hydrological, nutrient, and sediment budgets are presented for reservoir and lake waters Techniques for classification of lake water quality, assessment of the lake trophic state index, and of lake use support are presented Calculations for groundwater are given in Chapter 1.4 They include groundwater hydrology, flow in aquifers, pumping and its influence zone, setback zone, and soil remediation Well setback zone is regulated by the state EPA Determinations of setback zones are also included in the book Well function for confined aquifers is presented in Appendix B Hydraulics for environmental engineering is included in Chapter 1.5 This chapter covers fluid (water) properties and definitions; hydrostatics; fundamental concepts of water flow in pipes, weirs, orifices, and in open channel; and of flow measurements Pipe networks for water supply distribution systems and hydraulics for water and wastewater treatment plants are included Chapters 1.6 and 1.7 cover each unit process for drinking water and wastewater treatments, respectively The USEPA developed design criteria and guidelines for almost all unit processes These two chapters depict the integration of regulations (or standards) into water and wastewater design procedure Water fluoridation and the CT values are incorporated in Chapter 1.6 Biosolids are discussed in detail in Chapter 1.7 These two chapters are the heart Part 1, providing the theoretical considerations of unit processes, traditional (or empirical) design concepts, and integrated regulatory requirements Most calculations provided herein use U.S Customary units Readers who use the International System (SI) may apply the conversion factors listed in Chapter 1.1 Answers are also generally given in SI for most of problems solved using U.S units The current edition corrects certain computational, typographical, and grammatical errors found in the previous edition Drinking water quality standards, wastewater effluent standards, and several new examples have also been added The author also wishes to acknowledge Meiling Lin, Heather Lin, Robert Greenlee, Luke Lin, Kevin Lin, Jau-hwan Tzeng, and Lucy Lin for their assistance Any reader suggestions and comments will be greatly appreciated w.E asy En gin eer ing ne t Shun Dar Lin Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website Source: HANDBOOK OF ENVIRONMENTAL ENGINEERING CALCULATIONS Downloaded From : www.EasyEngineering.net CHAPTER 1.1 BASIC SCIENCE AND FUNDAMENTALS Shun Dar Lin ww CONVERSION FACTORS 1.3 PREFIXES FOR SI UNITS 1.8 w.E MATHEMATICS 1.8 3.1 Logarithms 1.9 3.2 Basic Math 1.10 3.3 Threshold Odor Measurement 1.13 3.4 Simple Ratio 1.14 3.5 Percentage 1.15 3.6 Significant Figures 1.19 3.7 Transformation of Units 1.21 3.8 Geometrical Formulas 1.26 4.6 Pumpage and Flow Rate 1.44 STATISTICS 1.50 5.1 Measure of Central Value 1.50 5.2 The Arithmetic Mean 1.50 5.3 The Medium 1.50 5.4 The Mode 1.50 5.5 Moving Average 1.51 5.6 The Geometric Mean 1.51 5.7 The Variance 1.52 5.8 The Standard Deviation 1.53 5.9 The Geometric Standard Deviation 1.54 5.10 The Student’s t Test 1.54 5.11 Multiple Range Tests 1.56 5.12 Regression Analysis 1.59 5.13 Calculation of Data Quality Indicators 1.65 asy En gi BASIC CHEMISTRY AND PHYSICS 1.31 4.1 Density and Specific Gravity 1.31 4.2 Chemical Solutions 1.33 4.3 pH 1.37 4.4 Mixing Solutions 1.40 4.5 Chemical Reactions and Dosages 1.42 nee rin g REFERENCES 1.69 CONVERSION FACTORS ne t The units most commonly used by water and wastewater professionals in the United States are based on the complicated U.S Customary System of Units However, laboratory work is usually based on the metric system due to the convenient relationship between milliliters (mL), cubic centimeters (cm3), and grams (g) The International System of Units (SI) is used in all other countries Factors for converting U.S units to the SI are given below (Table 1.1) to four significant figures EXAMPLE 1: Find degrees in Celsius of water at 68ЊF Solution: ЊC ϭ (ЊF Ϫ 32) ϫ 5 ϭ (68 Ϫ 32) ϫ ϭ 20 9 1.3 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website BASIC SCIENCE AND FUNDAMENTALS Downloaded From : www.EasyEngineering.net 1.4 CHAPTER 1.1 TABLE 1.1 Factors for Conversions U.S Customary units Multiply by Length inches (in) feet (ft) yard (yd) miles ww Area square inch (sq in, in2) square feet (sq ft, ft2) w.E asy acre (a) square miles (mi2) Volume cubic feet (ft3) cubic yard (yd3) gallon (gal) million gallons (Mgal) quart (qt) acre и feet (ac и ft) Weight pound (lb, #) grain ton (short) ton (long) gallons of water (US) Imperial gallon SI or U.S Customary units 2.540 0.0254 0.3048 12 0.9144 1.609 1760 5280 centimeters (cm) meters (m) m in m ft kilometers (km) yd ft 6.452 0.0929 144 4047 0.4047 43,560 0.001562 2.590 640 square centimeters (cm2) m2 in2 square meters (m2) hectare (ha) ft2 square miles km2 acres En 28.32 0.02832 7.48 6.23 1728 0.7646 3.785 0.003785 128 0.1337 3785 32 946 0.946 1.233 ϫ 10Ϫ3 1233 gin 453.6 0.4536 7000 16 0.0648 2000 0.9072 2240 8.34 10 liters (L) m3 US gallons (gal) Imperial gallons cubic inches (in3) m3 L m3 quarts (qt) pints (pt) fluid ounces (fl oz) ft3 m3 fl oz milliliters (mL) L cubic hectometers (hm3) m3 eer ing ne t grams (gm or g) kilograms (kg) grains (gr) ounces (oz) g lb tonnes (metric tons) lb lb lb Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website BASIC SCIENCE AND FUNDAMENTALS Downloaded From : www.EasyEngineering.net BASIC SCIENCE AND FUNDAMENTALS 1.5 TABLE 1.1 Factors for Conversions (contd.) U.S Customary units Unit weight ft3 of water pound per cubic foot (lb/ft3) Concentration parts per million (ppm) grain per gallon (gr/gal) ww Time day w.E hour minute Slope feet per mile SI or U.S Customary units 62.4 7.48 157.09 16.02 0.016 lb gallon newton per cubic meter (N/m3) kg force per square meter (kgf/m2) grams per cubic centimeter (g/cm3) 8.34 17.4 142.9 mg/L lb/Mgal mg/L lb/Mgal 24 1440 86,400 60 60 hours (h) minutes (min) seconds (s) s asy En gi Velocity feet per second (ft/sec) inches per minute miles per hour (mi/h) knot Multiply by Flowrate cubic feet per second (ft3/s, cfs) million gallons daily (MGD) gallons per minute (gpm) gallons per day MGD per acre и ft acre и feet per day Application (loading) rate pounds per square foot (lb/ft2) 0.1894 meter per kilometer 720 0.3048 30.48 0.6818 0.043 0.4470 26.82 1.609 0.5144 1.852 inches per minute meter per second (m/s) cm/s miles per hour (mph) cm/s m/s m/min km/h m/s km/h 0.646 448.8 28.32 0.02832 3.785 0.04381 157.7 694 1.547 3.785 0.06308 0.0000631 0.227 8.021 0.002228 3.785 0.4302 0.01427 4.8827 nee rin g million gallons daily (MGD) gallons per minutes (gpm) liter per second (L/s) m3/s m3/d (CMD) m3/s m3/h gallons per minute cubic feet per second (ft3/s) liters per minute (L/min) liters per second (L/s) m3/s m3/h cubic feet per hour (ft3/h) cubic feet per second (cfs, ft3/s) liters (or kilograms) per day gpm per cubic yard m3/s ne t kilograms per square meter (kg/m2) Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website BASIC SCIENCE AND FUNDAMENTALS Downloaded From : www.EasyEngineering.net 1.6 CHAPTER 1.1 TABLE 1.1 Factors for Conversions (contd.) U.S Customary units Multiply by pounds per 1000 square foot per day (lb/1000 ft2 и d) pounds per cubic foot (lb/ft3) pounds per 1000 cubic foot per day (lb/1000 ft3 и d) pounds per foot per hour (lb/ft и h) ww 1.4882 0.608 gallons per acre (gal/acre) million gallons per acre (Mgal/acre) million gallons per acre и ft (Mgal/acre и ft) gallons per square foot per day (gal/ ft2 и d) 0.00935 0.93526 0.43 gallons per minute per square foot (gpm/ ft2) square root of gpm per square foot (gal/min)0.5/ft2 gallons per day per foot (gal/d и ft) square foot per cubic foot (ft2/ ft3) cubic foot per gallon (ft3/gal) cubic foot per pound (ft3/lb) cubic foot per 1000 cubic foot per minute (ft3/1000 ft3 и min) Pressure pounds per square inch (lb/in2, psi) pounds per square foot (lb/ft2) pounds per cubic inch tons per square inch millibars (mb) inches of mercury 1.121 0.04074 0.04356 58.674 cubic meter per square meter per day (m3/m2 и d) Mgal/acre и d m3/m2 и d 2.7 (L/s)0.5/ m2 En Force pounds kilograms per square meter per day (kg/m2 и d) kilograms per cubic meter (kg/m3) kilograms per cubic meter per day (kg/m3 и d) kilograms per meter per hour (kg/m и h) kilograms per kilowatts per hour (kg/kW и h) kilograms per hectare per day (kg/ha и d) m3/ha m3/m2 gpm/yd3 16.017 0.016 pounds per horse power per hour (lb/hp и h) pounds per acre per day (lb/acre и d) w.E asy SI or U.S Customary units 0.00488 0.01242 3.28 7.48 0.06243 62.43 gin 0.4536 453.6 4.448 2.309 2.036 51.71 6895 0.0703 703.1 0.0690 4.882 47.88 0.01602 16.017 1.5479 100 345.34 0.0345 0.0334 0.491 m3/d и m m2/m3 m3/m3 m3/kg L/kg L/ m3 и eer ing kilograms force (kgf) grams(g) newtons (N) ne t feet head of water inches head of mercury mmHg newtons per square meter (N/m2) ϭ pascal (Pa) kgf/cm2 kgf/m2 bars kgf/m2 N/m2 (Pa) gmf/cm3 gmf/L kg/mm2 N/m2 kg/m2 kg/cm2 bar psi (lb/in2) Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website BASIC SCIENCE AND FUNDAMENTALS Downloaded From : www.EasyEngineering.net BASIC SCIENCE AND FUNDAMENTALS 1.7 TABLE 1.1 Factors for Conversions (contd.) U.S Customary units inches of water atmosphere pascal (SI) ww Mass and density slug w.E pound slug per foot3 density (␥) of water Multiply by SI or U.S Customary units 248.84 101,325 1013 14.696 29.92 33.90 1.0 1.0 ϫ 10Ϫ5 1.0200 ϫ 10Ϫ5 9.8692 ϫ 10Ϫ6 1.40504 ϫ 10Ϫ4 4.0148 ϫ 10Ϫ3 7.5001 ϫ 10Ϫ4 pascals (Pa) Pa millibars (1 mb ϭ 100 Pa) psi (lb/in2) inches of mercury feet of water N/m2 bar kg/m2 atmospheres (atm) psi (lb/in2) in, head of water cm head of mercury 14.594 32.174 0.4536 515.4 62.4 980.2 1.94 1000 1 kg lb (mass) kg kg/m3 lb/ft3 at 50ЊF N/m3 at 10ЊC slugs/ft3 kg/m3 kg/L gram per milliliter (g/mL) asy En gi specific wt () of water Viscosity pound-second per foot3 or slug per foot second square feet per second (ft2/s) Work British thermal units (Btu) hp-h kW-h Power horsepower (hp) kilowatts (kW) Btu per hour Temperature degree Fahrenheit (ЊF) (ЊC) 47.88 0.0929 1.0551 778 0.293 2545 0.746 3413 1.34 nee rin g newton second per square meter (Ns/m2) m2/s kilo joules (kj) ft lb watt-h heat required to change lb of water by 1ЊF Btu kW-h Btu hp-h 550 746 2545 3413 0.293 12.96 0.00039 ft lb per sec watt Btu per h Btu per h watt ft lb per hp (ЊF Ϫ 32) ϫ (5/9) (ЊC) ϫ (9/5) ϩ 32 ЊC ϩ 273.15 degree Celsius (ЊC) (ЊF) Kelvin (K) ne t Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website BASIC SCIENCE AND FUNDAMENTALS Downloaded From : www.EasyEngineering.net 1.8 CHAPTER 1.1 EXAMPLE 2: At a temperature of 4ЊC, water is at its greatest density What is the degree of Fahrenheit? Solution: ЊF ϭ (ЊC) ϫ ϩ 32 ϩ 32 ϭ 7.2 ϩ 32 ϭ 39.2 ϭ4ϫ PREFIXES FOR SI UNITS ww The prefixes commonly used in the SI system are based on the power 10 For example, a kilogram means 1000 grams, and a centimeter means one-hundredth of meter The most used prefixes are listed in Table 1.2, together with their abbreviations, meanings, and examples w.E asy MATHEMATICS Most calculations required by the water and wastewater plants operators and managers are depended on ordinary addition, subtraction, multiplication, and division Calculations are by hand, by calculator, or by a computer Engineers should master the formation of problems: daily operations require calculations of simple ratio, percentage, significant figures, transformation of units, flow rate, area and volume computations, density and specific gravity, chemical solution, and mixing of solutions En Miscellaneous Constants and Identities gin eer ing ϭ 3.14 (pi) e ϭ 2.7183 (Napierian) xo ϭ 1(x Ͼ 0) 0x ϭ (x Ͼ 0) TABLE 1.2 Prefixes for SI Units Prefix Abbreviation tera giga mega myria kilo hecto deka T G M my k h da deci centi millimicro nano pico femto atto d c m n p f a Multiplication factor 000 000 000 000 ϭ 1012 1000000000 ϭ 109 000 000 ϭ 106 10000 ϭ 104 1000 ϭ 103 100 ϭ 102 10 ϭ 101 ϭ 100 0.1 ϭ 10Ϫ1 0.01 ϭ 10Ϫ2 0.001 ϭ 10Ϫ3 0.000 001 ϭ 10Ϫ6 0.000 000 001 ϭ 10Ϫ9 0.000 000 000 001 ϭ 10Ϫ12 0.000 000 000 000 001 ϭ 10Ϫ15 0.000 000 000 000 000 001 ϭ 10Ϫ18 ne t Example km, kg meter (m), gram (g) cm mm, mg m, g Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net 4.98 CHAPTER 4.1 Aqueous solubility The aqueous solubility (S) of a compound is defined as the saturated concentration of the compound in water (mg COPC/L water) at a given temperature and pressure, usually at soil/water temperatures and atmospheric pressure 8.2 Henry’s Law Constant ww Henry’s law constant (H) is also referred to as the air-water partition coefficient, and is defined as the ratio of the partial pressure of a compound in air to the concentration of the compound in water at a given temperature under equilibrium conditions For organics (excluding PCDDs and PCDFs), H values were calculated from the following theoretical equation (Lyman, Reehl, and Rosenblast 1982) for consistency, using recommended MW, S, and Vp values provided in the USEPA HHRAP: Vp # MW H ϭ (1.52) S where H ϭ Henry’s law constant (atm ⋅ m3/mol) Vp ϭ Vapor pressure of COPC (atm) S ϭ Solubility of COPC in water (mg COPC/L water) w.E asy 8.3 Diffusivity of COPCs in Air and Water Diffusivity or diffusion coefficients in air (Da) and water (Dw) are used to calculate the liquid- or gasphase transfer of a COPC into a waterbody For organics (except PCDDs and PCDFs), diffusivity values were obtained directly from the CHEMDAT9 model chemical properties database (Worksheet DATATWO.WK1) (USEPA 1994d) For compounds not in the USEPA (1994d) database, diffusivity values were obtained by using the WATER8 (USEPA 1995d) model correlation equations for air and water diffusivities: For diffusivity values that were not available in these databases, Dw and Da values were calculated using the following equations cited and recommended for use in USEPA (1997g): En gin Da,i ϭ Dw,i ϭ 1.9 (MWi)2/3 22_10ϫ5 (MWi)2/3 eer ing ne t (1.53) For PCDDs and PCDFs, diffusivity values in air and water for (1) 2,3,7,8-TCDD were obtained from USEPA (1994e), and (2) 2,3,7,8-TCDF were obtained from USEPA (1995d) For all other congeners of PCDDs and PCDFs: A default Dw value of ϫ 10Ϫ06 cm2/s was used Da values were calculated using the following equation recommended by USEPA (1994a): MWy 0.5 Dx ϭ a b Dy MWx where (1.54) Dx,y ϭ Diffusivities in air of compounds x and y (cm2/s) MWx,y ϭ Molecular weights of compounds x and y (g/mol) Da values for PCDD congeners were calculated by using the Da value and MW for 2,3,7,8-TCDD Da values for PCDF congeners were calculated using the Da value and MW for 2,3,7,8-TCDF This approach is consistent with the methodology specified in USEPA (1994a) Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net AIR TOXIC RISK ASSESSMENT 4.99 8.4 Octanol/Water Partitioning Coefficient The n-octanol/water partitioning coefficient (Kow) is defined as the ratio of the solute concentration in the water-saturated n-octanol phase to the solute concentration in the n-octanol-saturated water phase 8.5 Soil Organic Carbon-Water Partition Coefficient ww The soil organic carbon-water partition coefficient (Koc) or the organic carbon normalized soil sorption coefficient is defined as the ratio of adsorbed compound per unit weight of organic carbon to the aqueous solute concentration Because of the soil mechanisms that are inherently involved, Koc values for the ionizing organics and nonionizing organics are discussed separately The partitioning of ionizing organic compounds can be significantly influenced by soil pH Because of the soil mechanisms that are inherently involved, we discuss Koc values for the ionizing organics and non-ionizing organics separately The soil organic carbon-water partition coefficient for ionizing organic compounds Ionizing organic compounds include amines, carboxylic acids, and phenols These compounds contain the functional groups that ionize under specific pH conditions, and include the following: w.E • Organic acids: (2,4,6-trichlorophenol; pentachlorophenol; 2,3,4,5-tetrachlorophenol; 2,3,4,6tetrachlorophenol; 2,4,5-trichlorophenol; 2,4-dichlorophenol; 2-chlorophenol; phenol; 2,4dimethylphenol; 2-methylphenol; 2,4-dinitrophenol; and benzoic acid) • Organic bases: (n-nitroso-di-n-propylamine; n-nitrosodiphenylamine, and 4-chloroaniline) asy En gi Koc values were estimated on the basis of the assumption that the sorption of ionizing organic compounds is similar to hydrophobic organic sorption, because the soil organic carbon is the dominant sorbent According to USEPA (1994c), for low pH conditions, these estimated values may overpredict sorption coefficients, because they ignore sorption to components other than organic carbon nee rin g The soil organic carbon-water partition coefficient for nonionizing organic compounds Nonionizing organic compounds are all other organic compounds not listed earlier as ionizing They include volatile organics, chlorinated pesticides, polynuclear aromatic hydrocarbons (PAHs), and phthalates The correlation between Koc and Kow can be improved considerably by performing separate linear regressions on two chemical groups USEPA (1994c) derives the following correlation equations from measured Koc values cited in USEPA (1994c) and USEPA (1996b): For most semivolatile nonionizing organic compounds log Koc ϭ 2.8 ϫ 10-4 ϩ (0.983 ϫ log Kow) (r2 ϭ 0.99) ne t (1.55a) For volatile nonionizing organics, chlorinated benzenes, and certain chlorinated pesticides log Koc ϭ 0.0784 ϩ (0.7919 ϫ log Kow) (r2 ϭ 0.97) (1.55b) For PCDDs and PCDFs, the following correlation equation is used to calculate Koc values, as cited by USEPA (1994a) log Koc ϭ log Kow Ϫ 0.21 (r2 ϭ 1.0) (1.55c) 8.6 Partitioning Coefficients Partition coefficients (Kd) describe the partitioning of a compound between sorbing material, such as soil, soil pore water, surface water, suspended solids, and bed sediments For organic compounds, Kd has been estimated to be a function of the organic-carbon partition coefficient and the fraction of organic carbon in the partitioning media For metals, Kd is assumed to be independent of the organic carbon in the partitioning media and, therefore, partitioning is similar in all sorbing media Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net 4.100 CHAPTER 4.1 Partitioning coefficients for soil-Water The soil-water partition coefficient (Kds) describes the partitioning of a compound between soil pore-water and soil particles, and strongly influences the release and movement of a compound into the subsurface soils and underlying aquifer Partitioning coefficients for suspended sediment-surface water The suspended sediment-surface water partition coefficient (Kdsw) describes the partitioning of a compound between surface water and suspended solids or sediments ww Partitioning coefficients for bottom sediment-sediment pore water The bed sediment-sediment pore-water partition coefficient (Kdbs) describes the partitioning of a compound between the bed sediments and bed sediment pore-water For organics (including PCDDs and PCDFs), soil organic carbon is assumed to be the dominant sorbing component in soils and sediments Therefore, Kd values were calculated using the following fraction organic carbon ( fOC) correlation equations: Kdsw ϭ foc,sw # K oc Kds ϭ foc,s # K oc w.E asy Kdbs ϭ foc,bs (1.56) #K oc The fraction organic carbon ( fOC), from literature searches USEPA (1993d), could range as follows: • 0.002 to 0.024 in soils for which a midrange value of foc,s ϭ 0.01 generally can be used • 0.05 to 0.1 in suspended sediments for which a midrange value of foc,sw ϭ 0.075 generally can be used • 0.03 to 0.05 in bottom sediments for which a midrange value of foc,bs ϭ 0.04 generally can be used En For metals (except mercury), Kd is governed by factors other than organic carbon, such as pH, redox, iron content, cation exchange capacity, and ion chemistry Values must be obtained directly from literature USEPA (1996b) provides values for Kd that are based on pH, and are estimated by using the MINTEQ2 model, which is a geochemical speciation model The MINTEQ2 model analyses were conducted under a variety of geochemical conditions and metal concentrations gin eer ing 8.7 Soil Loss Constant Due to Degradation Soil loss constant due to degradation (ksg) reflects loss of a compound from the soil by processes other than leaching Degradation rates in the soil media include biotic and abiotic mechanisms of transformation Abiotic degradation includes photolysis, hydrolysis, and redox reactions Hydrolysis and redox reactions can be significant abiotic mechanisms in soil (USEPA 1990) Degradation rates can be assumed to follow first order kinetics Therefore, the half-life (t1/2) of compounds can be related to the ksg as follows: Ideally, ksg is the sum of all biotic and abiotic rate constants in the soil Therefore, if the t1/2 for all of the mechanisms of transformation are known, the degradation rate can be calculated using ne t ksg ϭ 0.693 t 1/2 (1.57) Fraction of pollutant air concentration in the vapor phase For organics, the fraction of pollutant air concentration in the vapor phase (Fv) was calculated using the following equation: Fv ϭ Ϫ p EL cST ϩ cST (1.58) If the compound is a liquid at ambient temperatures (that is, when PLE is known), the above equation calculates Fv using the vapor pressure value recommended for that compound If the compound Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net AIR TOXIC RISK ASSESSMENT 4.101 is a solid at ambient temperatures (that is, when PSE is known), the following equation (Bidleman 1988) was used to calculate PLE from PSE, for use in the above equation: ln a where ww c PLE PSE R ⌬Sf ST Ta ϭ ϭ ϭ ϭ ϭ ϭ ϭ ⌬Sf (Tm Ϫ T) p EL b ϭ E T R PS (1.59) Junge constant ϭ 1.7 ϫ 10Ϫ04 (atm ⋅ cm) Liquid phase vapor pressure of compound (atm) Solid phase vapor pressure of compound (atm) Universal ideal gas constant (atm ⋅ m3/mol ⋅ K) Entropy of fusion [⌬Sf /R ϭ 6.79 (unitless)] Whitby’s average surface area of particulates (aerosols) Ambient air temperature (K)—assumed to be 25ЊC or 298 K This equation assumes that the Junge constant (c) is constant for all compounds However, c can depend on (1) the compound (sorbate) molecular weight, (2) the surface concentration for monolayer coverage, and (3) the difference between the heat of desorption from the particle surface and the heat of vaporization of the liquid-phase sorbate All metals (except mercury) are assumed to be present in the particulate phase and not in the vapor phase (Vp = 0), and assigned Fv values of zero Mercury and mercuric chloride are relatively volatile and exist in the vapor phase (USEPA 1997g) Fv values of 1.0 for mercury and 0.85 for mercuric chloride were estimated Methyl mercury is assumed not to exist in the air phase and, therefore, assigned an Fv of zero w.E asy En gi 8.8 Bioconcentration and Biotransfer Factors for Plants Root concentration factor The root concentration factor (RCF) is used to calculate the belowground transfer of contaminants from soil to a root vegetable The RCF was developed based on experiments conducted by Briggs et al (1982) which measured uptake of compounds into barley roots from growth solution For compounds with log Kow values of 2.0 and higher, we used the following correlation equation to obtain RCF values: nee rin g log (RCF) ϭ 0.77 log Kow Ϫ 1.52 (n ϭ 7, r ϭ 0.981) (1.60) ne t For compounds with log Kow values less than 2.0, we used the following correlation equation to obtain RCF values: log (RCF Ϫ 82) ϭ 0.77 log Kow Ϫ 1.52 (1.61) This equation estimates a RCF value in fresh weight (FW) units, which was then converted to dry weight (DW) units using a moisture content of 87 percent in root vegetables Kow values recommended in this HHRAP were used to calculate each RCF value For metals, including mercury, no referenced RCF values were available in published literature However, plant-soil biotransfer factors for root vegetables (Brrootveg) were available in the literature and, therefore, RCF values, which were used to calculate Brrootveg values, are not required for the metals Plant-soil bioconcentration factors in root vegetables The plant-soil bioconcentration factor for compounds in root vegetables (Brrootveg) accounts for uptake from soil to the belowground root vegetables or produce For organics, the following equation, obtained from USEPA (1995b), was used to calculate values for Brrootveg on a dry weight basis: Brrootveg ϭ RCF Kds (1.62) Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net 4.102 CHAPTER 4.1 Brrootveg values were calculated by dividing the RCF value with the Kds values provided in the main USEPA literature used in this Chapter (USEPA HHRAP) Brrootveg values for metals can also be obtained from the USEPA HHRAP ww Plant-soil Bioconcentration factors for aboveground produce and forage The plant-soil bioconcentration factor (Br) for aboveground produce accounts for the uptake from soil and the subsequent transport of COPCs through the roots to the aboveground plant parts As addressed in USEPA (1995b), the Br value for organics is a function of water solubility, which is inversely proportional to Kow The Br value for metals is a function of the bioavailability of the compounds in soil Plantsoil bioconcentration factors for aboveground produce (Brag) and forage (Brforage) For all organics including PCDDs and PCDFs, (1) the subscript ag represents aboveground produce which applies to exposed fruits and vegetables, and protected fruits and vegetables, and (2) the subscript forage represents forage, but the values also apply to silage and grain For metals, (1) aboveground fruits (both exposed and protected) are represented byBrag (fruit); (2) aboveground vegetables (both exposed and protected) are represented by Brag(veg), (3) forage is represented by Brforage, but the values also apply to silage, and (4) grains are represented by Brgrain For organics, the following correlation equations were used to calculate values for Brag and Brforage on a dry weight basis: w.E asy log Brag ϭ 1.588 Ϫ 0.578 (log K ow)(n ϭ 29, r ϭ 0.73) (1.63) log Brforage ϭ 1.588 Ϫ 0.578 (log K ow)(n ϭ 29, r ϭ 0.73) En Air-to-plant biotransfer factors for aboveground produce and forage The air-to-plant biotransfer factor is defined as the ratio of COPC concentration in aboveground plant parts to the COPC concentration in air Bv values for all organics and metals, were calculated only for aboveground exposed produce (both fruits and vegetables) Aboveground protected produce (both fruits and vegetables) and belowground produce are protected from air-to-plant transfer According to USEPA (1995b), root vegetables are assumed to be also protected from air-to-plant transfer For organics (excluding PCDDs and PCDFs), the Bvag and Bvforage can be calculated using the following correlation equations: gin eer ing H R Ϫ 1.654(r ϭ 0.957) RT rair # Bvol Bv ϭ (1 Ϫ fwater) # rforage log Bvol ϭ 1.065 log K ow Ϫ logQ where Bvol ϭ Volumetric air-to-plant biotransfer factor (fresh-weight basis) Bv ϭ Mass based air-to-plant biotransfer factor (dry-weight basis) air ϭ 1.19 g/L (Weast 1981) forage ϭ 770 g/L (Macrady and Maggard 1993) fwater ϭ 0.85 (fraction of forage that is water(Macrady and Maggard (1993)) (1.64) ne t 8.9 Biotransfer Factors for Animals The biotransfer factor for animals (Ba) is the ratio of COPC concentration in fresh weight animal tissue to the daily intake of COPC by the animal Biotransfer factors for beef and milk The main route of human exposure to many highly lipophilic compounds is through ingestion of contaminated agricultural products such as beef and milk The transfer of contaminants from environmental media (e.g., air, soil, water) and food (e.g Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net AIR TOXIC RISK ASSESSMENT 4.103 grain, sileage) into livestock products (e.g., beef, milk) has historically been either determined by direct measurement of contaminants in livestock products, or predicted using regression models (Biotransfer factors for beef (Babeef) and milk(Bamilk) Organic compounds When empirical data are lacking for biotransfer of organic chemicals, one of the most widely used approaches to predict contaminant transfer from environmental media and food to beef tissue and milk are the regression models developed by Travis and Arms (1988), which relate chemical octanol-water partition coefficient (Kow) to biotransfer into beef and milk These regressions, however, are hampered by the limited log Kow range and questions surrounding the validity of the underlying biotransfer data set In response, EPA developed a new methodology for predicting beef and milk biotransfer factors Using EPA’s updated methodology, we predicted biotransfer factors for organic chemicals with the following single equation: ww log Bafat ϭ –0.099 (log Kow )2 ϩ 1.07 log Kow – 3.56 where (n ϭ 305, r2 ϭ 0.8259) (1.65) Bafat ϭ Biotranfer factor [mg / kg fat] / [mg/d] Kow ϭ Octanol-water portioning coefficient [unitless] w.E Values for Ba fat were adjusted to account for the assumed fat content of milk and beef as shown below: Ba milk ϭ 10 log Ba fat ϫ 0.04 asy En gi Ba beef ϭ 10 log Ba fat ϫ 0.19 (1.66) The log Kow’s of the chemicals are used to derive the equation ranged from Ϫ0.67 to 8.2 Therefore, compounds with log Kow values less than Ϫ0.67 were assigned Ba beef and Ba milk values corresponding to a log Kow value of Ϫ0.67 At the high end of the range, compounds with log Kow values greater than 8.2 were assigned Ba beef and Ba milk values corresponding to a log Kow value of 8.2 nee rin g Highly metabolized organic compounds The BAfat might overestimate biotransfer of highly metabolized chemicals, producing an upper bound estimate for these chemicals Phthalates and PAHs fall within this group One way to account for this potential overestimation is to rely upon a metabolism factor to improve model predictions For example, EPA developed a metabolism factor of 0.01 (i.e., 99 percent of the chemical ingested is metabolized) for bis-ethylhexyl phthalate (BEHP) When this factor is applied to the biotransfer factors predicted using the regression equation recommended above for BEHP, the biotransfer factors are reduced by two orders of magnitude These metabolism-adjusted predicted biotransfer factors are close in magnitude to the empirically derived biotransfer factors found in the literature, which supports using this metabolism factor Unfortunately, EPA has not developed metabolism factors for other organic chemicals, due to limited availability of empirically derived data For those highly metabolized chemicals that don’t have metabolism factors, we still consider it reasonable to use estimated Ba values for the following reasons: ne t • Few chemicals have had all their degradation products identified • If identified, the degradation products may in fact be as toxic as, or even more toxic than, the parent compound (the degradation products of PAHs, for example, are toxic) Unless data demonstrates that all degradation products are nontoxic (as is the case for BEHP), the only way to address toxic degradation products in the HHRAP is to include their mass in the mass of the parent chemical • The metabolic degradation products may themselves be persistent For example, DDT is metabolized to DDD and DDE, which remain persistent It should also be noted that not all chemicals are metabolized at the same rate and may remain in animal tissue as the parent compound through establishment of steady state concentrations In fact, many of the chemicals in the biotransfer data set, that are actually well predicted, are metabolized to Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net 4.104 CHAPTER 4.1 other compounds DDT is metabolized to DDE, and lindane (used to derive the regression, but not in the HHRAP) is metabolized to many different compounds For DDT and lindane, biotransfer factors are well predicted using BAfat equation Lacking sufficient data to identify all degradation products, characterize all degradation products as nontoxic, and ensure that all potentially toxic degradation products are less persistent than the parent chemical, we consider it reasonably protective to use the Babeef and Bamilk values for the parent chemical as predicted, without adjustment If a highly metabolized chemical is found to drive the risk assessment, then we recommend re-evaluating the appropriateness of the Babeef and Bamilk values ww Ionizing organic compounds To improve bio-transfer factors (BTF) estimates for organic acids, the USEPA uses the first-order dissociation constant (pKa) to account for chemical ionization For these chemicals, Kow is a weighted value calculated based on the fraction of the chemical in the neutral form such that: Kow ϭ Kow n ϫ (FracNeutral ) ϩ Kowi ϫ ( Ϫ FracNeutral ) where w.E asy (1.67) Kow n ϭ Partition coefficient for the neutral species (unitless) Kow i ϭ Partition coefficient for the ionized species (mol/L) FracNeutral ϭ Fraction of neutral species present for organic acids (unitless) Accounting for the fraction of ionizable organics in the neutral form is important because Kow can vary considerably depending on pH The cow’s small intestine, where chemicals can be absorbed, has a near neutral pH Therefore, the neutral fraction is determined using a pH equal to in the following equation (Lee et al., 1990): where, En FracNeutral ϭ ϩ 10 pH Ϫ pKa gin pKa ϭ Acid dissociation constant (unitless) (1.68) eer ing If a value for log Kowi is not available, the USEPA estimates log Kowi assuming a ratio of log Kowi to log Kown of 0.015 This ratio is a conservative value developed by the USEPA to apply to organic acids without data for log Kowi (U.S EPA, 1996) Babeef and Bamilk values are for metals (except cadmium, mercury, selenium, and zinc) are calculated on a fresh weight basis, from Baes et al (1984) For cadmium, selenium, and zinc, USEPA (1995a) cited Ba values derived by dividing uptake slopes [(g COPC/kg DW tissue)/(g COPC/kg DW feed)], obtained from USEPA (1992b), by a daily consumption rate of 20 kg DW per day for beef and dairy cattle The HHRAP assumes that elemental mercury neither deposits onto soils nor transfers to aboveground plant parts Therefore, there is no transfer of elemental mercury into animal tissue Therefore, USEPA recommends Ba values of zero for elemental mercury This based on assumptions made regarding speciation and fate and transport of mercury from emission sources USEPA derived the Babeef and Bamilk values listed in the HHRAP database for mercuric chloride and methyl mercury from data in USEPA (1997b) .ne t Biotransfer factors for pork For organics (except PCDDs and PCDFs), biotransfer factors for pork (Bapork) values reported in the USEPA HHRAP were derived from Babeef values, assuming that pork is 23 percent fat and beef is 19 percent fat Therefore, Bapork values were calculated by multiplying Babeef values by their fat content ratio of 1.2 (23/19) This calculation is limited by the assumptions that: COPCs bioconcentrate in the fat tissues There is minimal effect from differences in metabolism and feeding characteristics between beef cattle and pigs Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net AIR TOXIC RISK ASSESSMENT 4.105 For PCDDs and PCDFs, Bapork values are calculated using the same methodology used to obtain Babeef values by USEPA (1995a) Assuming that milk is 3.5 percent fat and that pork is 23 percent fat, biotransfer factors for pork would be 6.57 times (23/3.5) higher than for milk Therefore, Bapork values were calculated by increasing Bamilk values by a factor of 6.57 This has the same effect as if the Bapork values were calculated by multiplying the Babeef values with the fat content ratio of 1.2 (23/19) between pork and beef, as was adopted for the remaining organic compounds ww Biotransfer factors for chicken and poultry eggs Biotransfer factors for chicken (Bachicken) and poultry eggs (Baegg) are expressed as the ratio of the COPC concentration in the fresh weight tissue to the COPC intake from the feed Biotransfer factors are calculated from bioconcentration factors for chicken and poultry eggs BCFs are expressed as the ratio of the COPC concentration in the fresh weight tissue to the COPC concentration in dry weight soil USEPA recommends deriving the biotransfer factors for chicken Bachicken values using the same method used to estimate Babeef values, modifying to reflect an assumed fat content of chicken of 14 percent, and eggs of percent Specifically, USEPA uses the equation to generate Bafat values, which were then adjusted to account for the assumed fat content of chicken and eggs as shown below: w.E Bachicken ϭ 10 log Bafat ϫ 0.14 Baeggs ϭ 10 log Bafat ϫ 0.08 (1.69) asy En gi These calculations are limited by the assumptions that: Contaminants bioconcentrate in the fat tissues Effects from differences in metabolism, digestive system, or feeding characteristics between beef cattle and chickens are minimal Please note that the scenario of principal concern for chicken and egg contamination is for home grown chickens The raising of home grown chickens would be characteristic of free range and semifree range housing conditions where poultry come in contact with soil, and possibly vegetation, insects, and benthic organisms The applicability of this scenario to commercial poultry operations characterized by housing conditions that not provide chickens access to soil would need to be assessed on a case-by-case basis nee rin g Bioconcentration and bioaccumulation factors for fish Bioconcentration and bioaccumulation factors for fish are used for various compounds, depending on the Kow value of the organic compound Bioconcentration factors for fish were used for organics (except PCDDs, PCDFs, and PCBs) with a log Kow value less than 4.0; and for metals (except lead and mercury) Bioaccumulation factors for fish were used for organics (except PCDDs, PCDFs, and PCBs) with a log Kow value greater than 4.0, lead, and mercuric compounds Biota-sediment accumulation factors for fish were used for PCDDs, PCDFs, and PCBs .ne t Bioconcentration factors for fish Bioconcentration factors for fish (BCFfish)is the ratio of the COPC concentration in fish to the COPC concentration in the water column where the fish is exposed It accounts for uptake of COPCs by fish from water passing across the gills BCF values for fish were used for all organic compounds with a log Kow of less than 4.0 (cutoff value with BAFfish) and for all metals, except lead and mercury, as cited in USEPA (1995b) This implies that the concentration of COPC in the fish is only due to water intake by the fish, and compounds with a log Kow of less than 4.0 are assumed not to bioaccumulate Our recommended BCF values don’t recognize differences in total versus dissolved water concentrations when calculating fish concentrations from BCFfish values for compounds with a log Kow of less than 4.0 Since, dissolved water concentrations is the major contributing factor from compounds with a log Kow of less than 4.0, all BCFfish values (regardless of whether they were derived using total or dissolved water concentrations) can be multiplied by the contaminant concentration in the dissolved water column (Cdw) to calculate fish concentrations This assumption is necessary because: Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net 4.106 CHAPTER 4.1 Literature data is often unclear if the water concentrations are dissolved or total concentrations Most of the literature reviewed indicated that laboratory experiments were conducted using filtered or distilled water; or the experiments were conducted using fresh water, but were filtered before analyses for water concentrations Meylan et al (1999) collected information on measured BCF and other key experimental details for 694 chemicals Log BCF was then regressed against log Kow, and chemicals with significant deviations from the line of best fit were analyzed by chemical structure The resulting algorithm classifies a substance as either nonionic or ionic, the latter group including carboxylic acids, sulfonic acids and their salts, and quaternary N compounds Log BCF for nonionics was estimated from log Kow and a series of correction factors if applicable; different equations apply for log Kow 1.0 to 7.0 and >7.0 (Meylan et al 1999) These equations are as follows: ww For log Kow Ͻ 1: log BCF ϭ 0.50 For log Kow to 7: log BCF ϭ 0.77 log Kow Ϫ 0.7 ϩ ⌺ Correction Factors For log Kow Ͼ 7: log BCF ϭ Ϫ1.37 log Kow ϩ14.4 ϩ ⌺ Correction Factors For log Kow Ͼ 10.5: log BCF ϭ 0.50 w.E asy For ionic compounds (carboxylic acids, sulfonic acids, and salts, compounds with N of +5 valence), were categorized by log Kow, and a log BCF in the range 0.5 to 1.75 was assigned as follows: For log Kow Ͻ 5: log BCF ϭ 0.50 For log Kow to 6: log BCF ϭ 0.75 For log Kow to 7: log BCF ϭ 1.75 For log Kow to 9: log BCF ϭ 1.0 For log Kow Ͼ 9: log BCF ϭ 0.50 En gin USEPA assumes that BCFfish values calculated using the above equations were: Based on dissolved water concentrations Not lipid-normalized eer ing Bioaccumulation factors for fish Bioaccumulation factors for fish (BAFfish)is the ratio of the COPC concentration in fish to the COPC concentration in the water body where the fish are exposed The BAFfish accounts for uptake of COPCs by fish from water and sediments passing across the gills, and from consumption of various foods including plankton, daphnids, and other fish BAFfish was used for organic compounds (except PCBs, PCDDs, and PCDFs) with a log Kow greater than 4.0, lead, and mercuric compounds For compounds with a log Kow of greater than or equal to 4.0, COPCs can significantly partition into the suspended sediment organic carbon (or particulate phase) of the water column Therefore, BAF values should be based on total (dissolved and suspended) water column concentrations The following equation cited in USEPA (1995f ) is recommended to convert the BAF based on total water concentrations to a BAF based on dissolved water concentrations: ne t ffd ϭ where (DOC) (K ow) 1ϩ ϩ (POC)(K ow) 10 (1.70) f fd ϭ fraction of COPC that is freely dissolved in water DOC ϭ concentration of dissolved organic carbon, kg organic carbon/L water POC ϭ concentration of particulate organic carbon, kg organic carbon/L water Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net AIR TOXIC RISK ASSESSMENT 4.107 Since, the model was derived from a study conducted at Lake Ontario, DOC and POC values for Lake Ontario were used Values cited in USEPA (1995f) were: DOC ϭ ϫ 10Ϫ6 kg/L POC ϭ 7.5 ϫ 10Ϫ9 kg/L (1.71) A BAF based on dissolved water concentrations can be calculated from a BAF based on total water concentrations as follows: BAF (dissolved) ϭ BAF (total) Ϫ1 ffd (1.72) ww For all organics (except PCBs, PCDDs, and PCDFs) with a log Kow greater than or equal to 4.0, the FCM, which accounts for accumulation through the food chain in addition to water, becomes greater than Therefore, a BAFfish, which takes the food chain into consideration, is more appropriate than a BCFfish For all organics with a log Kow greater than or equal to 4.0, BAFs were derived using one of following these methods: w.E BAF ϭ Field measured BAF or BCF, adjusted for dissolved water concentrations BAF ϭ Laboratory measured BCF multiplied by a FCM for either trophic level or fish asy En gi Both field and laboratory measured values were derived from various literature sources cited in USEPA (1999a) FCMs were obtained from USEPA (1995f ) For lead, the food-chain multiplier becomes greater than one; therefore, a BAF is more appropriate The BAFfish value reported in this HHRAP for lead was obtained as a geometric mean from various literature sources described in USEPA (1999a) Since metals are assumed insoluble under neutral conditions, the dissolved and total water concentrations are almost equal However, for consistency, the BAFfish value for lead was adjusted for dissolved fractions nee rin g Biota-sediment accumulation factor for fish For PCDDs, PCDFs, and PCBs, bioaccumulation factors for fish (BSAFfish)values should be used instead of BAFs for fish BSAFfish values reported in this HHRAP were obtained from USEPA (1994a) BSAFfish accounts for the transfer of COPCs from the bottom sediment to the lipid in fish Homologue group BSAFfish values obtained from USEPA (1994a) were either measured or estimated values that were based on a whole fish lipid content of percent and an organic carbon content of percent The BSAFfish values reported in this HHRAP are consistent with the values presented in primary guidance documents HUMAN HEALTH BENCHMARKS ne t The following sections discuss carcinogenic and noncarcinogenic toxicity benchmarks of compounds The toxicity information provided in the HHRAP is for informational purposes to help permitting authorities explain the basis for selecting contaminants of concern Since toxicity benchmarks and slope factors may change as additional toxicity research is conducted, permitting authorities should consult with the most current version of EPA’s Integrated Risk Information System (IRIS) and Health Effects Assessment Summary Tables(HEAST) before completing a risk assessment to ensure that the toxicity data used in the risk assessment is based upon the most current agency consensus 9.1 Reference Dose (Rfd) and Reference Concentration (RfC) Reference dose is defined as a daily intake rate of a compound estimated to pose no appreciable risk of deleterious effects over a specific exposure duration (USEPA 1989e) Reference concentration is Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net 4.108 CHAPTER 4.1 defined as the concentration of a compound estimated (with uncertainty spanning perhaps an order of magnitude) to pose no appreciable risk of deleterious effects over a specific exposure duration (USEPA 1989e) 9.2 Oral Cancer Slope Factor, Inhalation CSF, and Inhalation Unit Risk Factor Oral cancer slope factor (CSF), inhalation CSF, and inhalation unit risk factor (URF) values for all compounds can be obtained from IRIS and HEAST 9.3 Explanation of Calculated Toxicity Benchmark Values ww The preference for health benchmarks is to obtain values from IRIS or HEAST The following methodology was used to calculate missing benchmarks using available benchmarks that are based on route-to-route extrapolation: Oral RfDs presented in IRIS/HEAST/EPA reviewed documents were used if available missing oral RfDs were calculated from the RfC assuming route-to-route extrapolation using the following equation: w.E asy Oral Rf D ϭ RfC # 20 m3/d 70 kg BW (1.73) Oral CSFs presented in IRIS/HEAST/EPA reviewed documents were used when available In the case of missing oral CSFs: En a Oral CSF ϭ Inhalation CSF, or gin b Oral CSF ϭ Inhalation CSF calculated from Inhalation URF assuming route-to-route extrapolation For inhalation URFs, values were obtained from IRIS/HEAST/EPA reviewed documents If the inhalation URFs were not available they were calculated from oral CSF, using the following equation: Oral CSF # 20 m3/d (1.74) Inhalation URF ϭ 70 kgx 1000 µg>mg eer ing ne t The inhalation CSFs presented in IRIS/HEAST/EPA should be used when available a If no inhalation CSF was available; it was calculated from inhalation URF, using the following equation: Inhalation URF # 70 kg (1.75) Inhalation CSF ϭ ϫ 1000 µg/mg 20 m3/d b If no inhalation URF was available; the following was assumed based on route-to-route extrapolation: Inhalation CSF ϭ Oral CSF (1.76) 10 TERMINOLOGY AND VARIABLE IN HUMAN HEALTH RISK ASSESSMENT air forage ϭ Density of air (g/cm3) ϭ Density of forage (g/cm3) Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net AIR TOXIC RISK ASSESSMENT ww Babeef Bachicken Baegg Bamilk Bapork BAFfish ϭ ϭ ϭ ϭ ϭ ϭ BCFfish Brag ϭ ϭ Brforage/silage ϭ Brgrain ϭ Brrootveg ϭ BSAFfish ϭ Bvol ϭ Bvag ϭ w.E Bvforage/silage ϭ c Da Dw foc,bs foc,s foc,sw fwater Fv Fw H CSFInhalation URFInhalation Kds Kdsw ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ Kdbs ϭ Kow Koc ksg MW pLE pSE Oral CSF R RCF RfC RfD Rp S ⌬Sf ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ 4.109 Biotransfer factor in beef (mg COPC/kg FW tissue)/(mg COPC/d) Biotransfer factor in chicken (mg COPC/kg FW tissue)/(mg COPC/d) Biotransfer factor in eggs (mg COPC/kg FW tissue)/(mg COPC/d) Biotransfer factor in milk (mg COPC/kg FW tissue)/(mg COPC/d) Biotransfer factor in pork (mg COPC/kg FW tissue)/(mg COPC/d) Bioaccumulation factor in fish (mg COPC/kg FW tissue)/(mg COPC/L total water column) Bioconcentration factor in fish (L/kg FW or unitless) Plant-soil bioconcentration factor in aboveground produce (g COPC/g DW plant)/(g COPC/g DW soil) (unitless) Plant-soil bioconcentration factor in forage and silage (g COPC/g DW plant)/(g COPC/g DW soil) (unitless) Plant-soil bioconcentration factor in grain (g COPC/g DW grain)/(g COPC/g DW soil) unitless Plant-soil bioconcentration factor for belowground produce (g COPC/g DW plant)/(g COPC/g DW soil) (unitless) Biota-sediment accumulation factor in fish (mg COPC/kg lipid tissue)/(mg COPC/kg sediment) (unitless) Volumetric air-to-leaf biotransfer factor in leaf (g COPC/L FW plant)/(g COPC/L air) (unitless) COPC air-to-plant biotransfer factor for aboveground produce (g COPC/g DW plant)/(mg COPC/g air) (unitless) Air-to-plant biotransfer factor in forage and silage (g COPC/g DW plant)/(g COPC/g air) (unitless) Junge constant = 1.7 ϫ 10Ϫ04 (atm.cm) Diffusivity of COPC in air (cm2/s) Diffusivity of COPC in water (cm2/s) Fraction of organic carbon in bottom sediment (unitless) Fraction of organic carbon in soil (unitless) Fraction of organic carbon in suspended sediment (unitless) Fraction of COPC in water (unitless) Fraction of COPC air concentration in vapor phase (unitless) Fraction of wet deposition that adheres to plant surfaces (unitless) Henry’s law constant Inhalation cancer slope factor (mg/kg ⋅ d)Ϫ1 Inhalation unit risk factor (g/m3)-1 Soil-water partition coefficient (mL water/g soil OR cm3 water/g soil ) Suspended sediment-surface water partition coefficient (L water/kg suspended sediment OR cm3 water/g suspended sediment) Bed sediment-sediment pore water partition coefficient (L water/kg bottom sediment OR cm3 water/g bottom sediment) Octanol/water partitioning coefficient (mg COPC/L octanol)/(mg COPC/L octanol) Soil organic carbon-water partition coefficient (mL water/g soil) COPC soil loss constant due to biotic and abiotic degradation (yearϪ1) Molecular weight of COPC (g/mol) Liquid-phase vapor pressure of COPC (atm) Solid-phase vapor pressure of COPC (atm) Oral cancer slope factor (mg/kg ⋅ d)Ϫ1 Universal gas constant (atm.m3/mol ⋅ K) Root concentration factor (mg COPC/g DW plant)/(mg COPC/mL soil water) Reference concentration (mg/m3) Reference dose (mg/kg/d) Interception factor of edible portion of plant (unitless) Solubility of COPC in water (mg COPC/L water) Entropy of fusion [⌬Sf /R ϭ 6.79 (unitless)] asy En gi nee rin g ne t Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net 4.110 CHAPTER 4.1 ST t1/2 Ta Tm TEF Vp ϭ ϭ ϭ ϭ ϭ ϭ ϭ ϭ Whitby’s average surface area of particulates (aerosols) 3.5 ϫ 10Ϫ06 cm2/cm3 air for background plus local sources 1.1 ϫ 10Ϫ05 cm2/cm3 air for urban sources Half-time of COPC in soil (days) Ambient air temperature (K) Melting point temperature (K) Toxicity equivalency factor (unitless) Vapor pressure of COPC (atm) 11 REFERENCES ww Agricultural Research Service 1994 Personal communication regarding the dry weight fraction value for hay between G F Fries, Glenn Rice, and Jennifer Windholz, USEPA Office of Research and Development March 22 Baes, C F., R D Sharp, A L Sjoreen, and R W Shor 1984 Review and Analysis of Parameters and Assessing Transport of Environmentally Released Radionuclides through Agriculture ORNL-5786 Oak Ridge National Laboratory Oak Ridge, Tennessee September Baes, C.F., R.D Sharp, A L Sjoreen and R W Shor 1984 A Review and Analysis of Parameters for 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731–744 Miller, R W and D T Gardiner 1998 In: Soils in Our Environment J U Miller, Ed Prentice Hall Upper Saddle River, NJ pp 80–123 National Academy of Sciences (NAS) 1987 Predicting Feed Intake of Food-Producing Animals National Research Council, Committee on Animal Nutrition, Washington, D.C NC DEHNR 1997 Final NC DEHNR Protocol for Performing Indirect Exposure Risk Assessments for Hazardous Waste Combustion Units January Ng, Y C., C S Colsher and S E Thomson 1982 Transfer Coefficients for Assessing the Dose from Radionuclides in Meat and Eggs U.S Nuclear Regulatory Commission Final Report NUREG/CR-2976 Ogata, M K., Y Ogino Fijusaw and E Mano 1984 Partition Coefficients as a Measure of Bioconcentration Potential of Crude Oil Compounds in Fish and Shellfish Bulletin of Environmental Contaminant Toxicology vol 33 pp 561 Pennington, J A T 1989 Food Values of Portions Commonly Used 15th edn Harper and Row New York Petreas, M X., L R Goldman, D G Hayward, R Chang, J Flattery, T Wiesmuller, R D Stephens, D M Fry and C Rappe 1991 Biotransfer and Bioaccumulation of PCDD/PCDFs from Soils: Controlled Exposure Studies of Chickens Chemosphere vol.23 pp 1731–1741 Research Triangle Institute (RTI) 1992 Preliminary Soil Action Level for Superfund Sites Draft Interim Report Prepared for USEPA Hazardous Site Control Division, Remedial Operations Guidance Branch Arlington, Virginia EPA Contract 68-W1-0021 Work Assignment No B-03, Work Assignment Manager Loren Henning December Riederer, M 1990 Estimating Partitioning and Transport of Organic Chemicals in the Foliage/Atmosphere System: Discussion of a Fugacity-Based Model Environmental Science and Technology vol 24: 829–837 Shor, R W., C F Baes and R D Sharp 1982 Agricultural Production in the United States by County: A Compilation of Information from the 1974 Census of Agriculture for Use in Terrestrial Food-Chain Transport and Assessment Models Oak Ridge National Laboratory Publication ORNL-5786 Stephens, R D., M X Petreas and D G Hayward 1992 Biotransfer and Bioaccumulation of Dioxins and Dibenzofurans from Soil Hazardous Materials Laboratory, California Department of Health Services Berkeley, California Stephens, R D., M X Petreas and D G Hayward 1995 Biotransfer and Bioaccumulation of Dioxins and Furnas from Soil: Chickens as a Model for Foraging Animals The Science of the Total Environment vol 175 pp 253–273 Travis, C C and A O Arms 1988 Bioconcentration of Organics in Beef, Milk, and Vegetation Environmental Science and Technology vol 22 pp 271–274 w.E asy En gi nee rin g ne t Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website AIR TOXIC ASSESSMENT Downloaded From :RISK www.EasyEngineering.net 4.112 CHAPTER 4.1 ww U.S Bureau of the Census 1987 Statistical Abstract of the United States: 1987 107th edn Washington, D.C U.S Department of Agriculture (USDA) 1994 Noncitrus Fruits and Nuts 1993 Summary National Agricultural Statistics Service, Agricultural Statistics Board, Washington, D.C Fr Nt 1–3 (94) U.S Department of Agriculture (USDA) 1994 Personal Communication Between G F Fries, and Glenn Rice and Jennifer Windholtz, U.S Environmental Protection Agency, Office of Research and Development Agricultural Research Service March 22 U.S Department of Agriculture (USDA) 1994 Personal Communication Regarding Soil Ingestion Rate for Dairy Cattle Between G F Fries, Agricultural Research Service, and Glenn Rice and Jennifer Windholtz, USEPA, Office of Research and Development March 22 U.S Department of Agriculture (USDA) 1994 Vegetables 1993 Summary National Agricultural Statistics Service, Agricultural Statistics Board Washington, D.C Vg 1–2 (94) U.S Department of Agriculture (USDA) 1997 Predicting Soil Erosion by Water: A Guide to Conservation Planning With the Revised Universal Soil Loss Equation (RUSLE) Agricultural Research Service, Agriculture Handbook Number 703 January USEPA 1982 Pesticides Assessment Guidelines Subdivision O Residue Chemistry Office of Pesticides and Toxic Substances, Washington, D.C EPA/540/9-82-023 USEPA 1985 Water Quality Assessment: A Screening Procedure for Toxic and Conventional Pollutants in Surface and Groundwater Part I (Revised 1985) Environmental Research Laboratory Athens, Georgia EPA/600/6-85/002a September USEPA 1988 Superfund Exposure Assessment Manual Office of Solid Waste Washington, D.C April USEPA 1990 Interim Final Methodology for Assessing Health Risks Associated with Indirect Exposure to Combustor Emissions Environmental Criteria and Assessment Office Office of Research and Development EPA 600-90-003 January USEPA 1990 Exposure Factors Handbook March USEPA 1992 Addendum to the Methodology for Assessing Health Risks Associated with Indirect Exposure to Combustor Emissions External Review Draft Office of Research and Development Washington, D.C November USEPA 1992 Estimating Exposure to Dioxin-Like Compounds Draft Report Office of Research and Development Washington, D.C EPA/600/6-88/005b USEPA 1992 Technical Support Document for Land Application of Sewage Sludge Volumes I and II Office of Water Washington, D.C EPA 822/R-93-001a USEPA 1993 Addendum to the Methodology for Assessing Health Risks Associated with Indirect Exposure to Combustor Emissions Working Group Recommendations Office of Solid Waste Office of Research and Development Washington, D.C September 24 USEPA 1993 Addendum to the Methodology for Assessing Health Risks Associated with Indirect Exposure to Combustor Emissions External Review Draft Office of Research and Development Washington, D.C November USEPA 1993 Derivation of Proposed Human Health and Wildlife Bioaccumulation Factors for the Great Lakes Initiative Office of Research and Development, U.S Environmental Research Laboratory Duluth, Minnesota March USEPA 1993 Review Draft Addendum to the Methodology for Assessing Health Risks Associated with Indirect Exposure to Combustor Emissions Office of Health and Environmental Assessment Office of Research and Development EPA-600-AP-93-003 November 10 USEPA 57 Federal Register 20802 1993 Proposed Water Quality Guidance for the Great Lakes System April 16 USEPA 1994 Draft Guidance for Performing Screening Level Risk Analyses at Combustion Facilities Burning Hazardous Wastes Attachment C, Draft Exposure Assessment Guidance for RCRA Hazardous Waste Combustion Facilities Office of Emergency and Remedial Response Office of Solid Waste April 15 USEPA 1994 Draft Guidance for Performing Screening Level Risk Analysis at Combustion Facilities Burning Hazardous Wastes Attachment C, Draft Exposure Assessment Guidance for RCRA Hazardous Waste Combustion Facilities April 15 USEPA 1994 Draft Exposure Assessment Guidance for RCRA Hazardous Waste Combustion Facilities Office of Solid Waste and Emergency Response EPA-530-R-94-021 April w.E asy En gin eer ing ne t Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright © 2007 The McGraw-Hill Companies All rightsFrom reserved Downloaded : www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website ... Downloaded From : www.EasyEngineering.net Source: HANDBOOK OF ENVIRONMENTAL ENGINEERING CALCULATIONS Downloaded From : www.EasyEngineering.net P A ● ● R T ● ● CALCULATIONS OF WATER QUALITY ASSESSMENT... Waste Calculations 07 08 09 w.E asy Wastewater Engineering Thermodynamics used in Environmental Engineering En gi Basic Combustion and Incineration 10 Practical Design of Waste Incineration 11 Calculations. .. www.EasyEngineering.net Any use is subject to the Terms of Use as given at the website Source: HANDBOOK OF ENVIRONMENTAL ENGINEERING CALCULATIONS Downloaded From : www.EasyEngineering.net CHAPTER 1.1 BASIC SCIENCE