CE 510 Hazardous Waste Engineering Department of Civil Engineering Southern Illinois University Carbondale Instructors: Jemil Yesuf and Dr. L.R. Chevalier Lecture Series 3: Hazardous Waste Properties and Classification Course Goals Review the history and impact of environmental laws in the United States Understand the terminology, nomenclature, and significance of properties of hazardous wastes and hazardous materials Develop strategies to find physical and chemical properties, i.e., water solubility, density, flammability, and toxicity for hazardous compounds Elucidate procedures for describing, assessing, and sampling hazardous wastes at industrial facilities and contaminated sites Predict the behavior of hazardous chemicals in surface impoundments, soils, groundwater and treatment systems Assess the toxicity and risk associated with exposure to hazardous chemicals Apply scientific principles and process designs of hazardous wastes management, remediation and treatment Concentration - mg/L to ppm In environmental engineering, we are sometimes dealing with dilute aqueous solutions. In such a case, we assume that the substance does not change the density of water. Based on this assumption, we can relate mg/L to ppm. Concentration - mg/L to ppm From the density of water, we know that 10-3 ml of water weighs 1 mg. w 1 g ml 1000 m g / m l Concentration - mg/L to ppm Substituting the volume of water for the mass of water in 1 mg/L we obtain the following: 1 mg L 1 mg 1 kg 1 mg 6 10 mg 1 part per million 1 ppm THEREFORE, IN OUR DILUTE AQUEOUS SOLUTIONS WE COMMONLY INTERCHANGE mg/L WITH ppm Class Example A 500-L tank contains 255 mg/L 2,4,6trichlorophenol dissolved in hexane. What is the trichlorophenol concentration in ppm? Assume the temperature of the system is 20°C. Specific gravity of Hexane is 0.6603 (Appendix C) Solution Mass of trichlorophenol dissolved in hexane is: (255 mg/L)(500L) = 127,500 mg = 0.128 kg Mass of hexane as a solvent is: (500 L)(0.6603)(1000kg/1000L) = 330 kg Therefore, concentration of trichlorophenol in hexane is: (127,500 mg)/(330 kg) = 386 mg/kg = 386 ppm ......end of example Concentration - air In dilute aqueous solutions, ppm is a mass- to-mass ratio In air, ppm is a volume-to-volume ratio Changes in temperature and pressure do not change the volume of the pollutant gas to the volume of the air that contains it i.e. we can compare ppm from Washington D.C. to Denver without further conversion We will define the Ideal Gas Law to further understand this… Ideal Gas Law P V nR T w here P absolute pressure atm or kP a V volum e L or m 3 n m ass [ m ol ] T absolute tem perature K R proportion ality const . or ideal gas const . 0 .0821 L atm / K m ol 8 .3143 J / K m ol Example How much volume in liters will one mole of any ideal gas occupy at standard temperature and pressure (STP). Note: STP is 273.13°K and 101.325 kPa (0°C and 1 atm). Solution Use the ideal gas law to solve for volume. Note: J = N. m Pa = N/m2 N m m ole K K m ole V N m 1 m 3 2 m ole 8 .3143 273.16 101.325 kP a 1000 P a kP a J K m ole K 1000 L m 3 22 .414 L ......end of example Solution Similarly, if we consider the volume at 25°C N m mole K K mole 3 V m N m 2 1mole 8 . 3143 J K mole 273 25 K 1000 Pa 101 . 325 kPa 1000 kPa L m 3 24 . 45 L ......end of example Example The chemical para-dichlorobenzene (p-DCB) is used in an enclosed area. At 20C (68F) the saturated vapor pressure of 1,4-DCB is 5.3 x 10-4 atm. What would be the concentration in the air of the enclosed area (units of g/m3) at 20C ? Solution Rearrange the Ideal Gas Law to solve for the concentration of 1,4-DCB in the air n V P RT 5 . 3 10 4 atm L atm o 0 . 08205 293 K mol K g 5 mol 1000 L 2 . 2 10 147 3 L m mol 3 .2 g m 3 Example Anaerobic microorganisms metabolize organic matter to carbon dioxide and methane gases. Estimate the volume of gas produced (at atmospheric pressure and 25° C) from the anaerobic decomposition of 2 moles of glucose. The reaction is: C 6 H 12 O 6 3CH 4 3CO 2 Solution Each mole of glucose produces 3 moles of methane and 3 moles of carbon dioxide gases, for a total of 6 moles. Therefore, 2 moles of glucose produces a total of 12 moles. The entire volume is then L atm 12 mol 0 . 0821 298 K nRT K mol V 1 atm P 294 L Note: The volume of 1 mole of any gas is the same. Thus, 1 mole of carbon dioxide gas is the same volume of 1 mole of methane gas. Concentration - Air Correction factor for conditions other than STP L T2 V 22 . 414 mole 273 K ppm volume 101 . 325 kPa P2 3 conta min ant volume (m ) 3 air 10 6 (m ) Incorporate this factor in order to report as ppm Concentration - Air Based on these two equations, we can convert mg/L (g/m3) to ppm using C ppm RT 6 C 10 PM M is the molecular weight in g/mole Concentration is g/m3 Example Convert 80 mg/m3 of SO2 in 1 m3 of air, 25° C, 101.325 kPa to ppm Solution C ppm RT 6 C 10 PM 80 10 3 30 . 6 ppm J 8 . 314 273 25 K K mol 6 10 Pa g 101 . 325 kPa 1000 64 kPa mol Water Solubility the maximum concentration of a substance that will dissolve in water at equilibrium at a given temperature and pressure Controls Concentration of a chemical in groundwater Proportion that exists as a free product Partitioning into solids Inversely related to sorptivity, bioaccumulation, and volatilization Affects a number of other pathways such as biodegradation, photolysis, chemical oxidation Together with another chemical parameter, Kow, determine the fate of chemicals in the environment Equilibrium Most chemical reactions are to some extent reversible when the rates of reaction are the same, i.e. the products are formed on the left at the same rate at which they are formed on the right. In such a case, the reaction is said to have reached equilibrium. Generalized Reversible Reaction aA bB cC dD where a , b , c , d # of molecules A , B , C , D chemical reaction same time species in both directions at the Generalized Reversible Reaction aA bB cC dD C D a b A B c d K Here, K is the equilibrium constant Provides the ratio of the concentration of individual reactants and products for any reaction at equilibrium Use this equation with a degree of caution Valid only when chemical equilibrium is established Natural systems are often subject to constantly changing inputs Some reactions occur very slowly Equilibrium may never be established Important Equilibrium Processes in Environmental Systems Acids and bases Dissolved and precipitated chemicals Pure compounds and air (volatilization) Chemicals dissolved in water and air (Henry’s Law) Chemicals dissolved in water and adsorbed on a solid (adsorption and ion exchange) Acid-Base Chemistry Among the most important in environmental engineering Waste must be neutralized Aquatic life sensitive to changes The concentration of acid/base is given by the pH By controlling pH, unwanted substances may be driven out of solution as gases or precipitates Acid-Base Chemistry HA H A We’ll evaluate this equation further later. First, lets consider the dissociation of water and the definition of pH Acid-Base Chemistry Water dissociates slightly into Hydrogen Ions (H+) Hydroxide Ions (OH-) H 2O H H OH H 2 O OH K Acid-Base Chemistry H O H K pH= -log [H+] [H+] = 10-pH w 10 14 @ 25 C Example What percentage of total ammonia (i.e. NH3 + NH4) is present as NH3 at a pH of 7? The pKa for NH4+ is 9.3. NH 4 H K a 10 9 .3 NH 3 NH 3 H NH 4 Solution The problem is asking: NH 3 NH 3 NH 4 100 Solution The problem is asking: NH 3 NH 3 NH 4 100 However, this expression has two unknowns. Therefore, we need a second equation. ????? Solution The problem is asking: NH 3 NH 3 NH 4 100 K a 10 9 .3 NH 3 H NH 4 Solution K a 10 9 .3 NH 3 H NH NH 10 NH 4 7 K a 10 9 .3 3 4 Recall, pH=7 means [H] = 10-7 Solution K a 10 Therefore: 9 .3 NH 3 10 7 NH 4 NH 200 NH 4 3 Solution NH 3 100 NH 3 NH 4 NH 3 100 % NH 3 200 NH 3 0 .5 % Acid-Base Chemistry Relationship between pH and pKa Consider a generalized acid reaction HA H A Acid-Base Chemistry H A Ka Take the logarithm HA log K a log H log A HA or A pH pK a log HA Henderson-Hasselbalch equation Example How is pH related to pKa when the acid is 50% ionized? (i.e. [A-] = [HA]) Solution A pH pK a log HA pK a log 1 or pH pK a ......end of example Solubility Product Solid Chemical Dissolved Chemical Equilibrium Constant Notation: Solubility Product (Ksp) Solubility Product All complexes are soluble in water to a certain extent Likewise, all complexes are limited by how much can be dissolved in water Example NaCl very soluble AgCl only a small amount will go into solution Solubility Product Visualize a solid compound being placed in distilled water Some of the compound will go into solution At some time, no more of the compound will dissolve At this point, equilibrium is reached may take seconds may take centuries Solubility Product Consider the following NaCl s Na Cl The solid form, NaCl, may be dissociating into its ionic components (dissolution) OR The ionic components may be recombining into the solid form (precipitation) Solubility Product The conditions of equilibrium can be expressed in an equilibrium or mass action equation for a generalized reaction. A x B y xA yB Solid Compound A x B y A x By K Ionic Components Solubility Product The brackets indicate molar concentrations K is an equilibrium constant for a given substance in pure water at a given temperature At equilibrium, the solid phase does not change concentration because dissolution and precipitation are equal. Solubility Product The brackets indicate molar concentrations K is an equilibrium constant for a given substance in pure water at a given temperature At equilibrium, the solid phase does not change concentration because dissolution and precipitation are equal. A x B y K s const . A B KK s K sp x y Solubility Product Supersaturated Solution Created by dissolving a solid at an elevated temperature and allowing it to cool Once cooled, precipitation may not occur, although the solution is not at equilibrium Precipitation will occur if the reaction vessel is shaken or otherwise disturbed Solubility Product Unsaturated Solution Not at equilibrium Can dissolve more solid Saturated Solution At equilibrium Cannot dissolve more solid unless the temperature or pressure is increased Solubility Product A B x y K sp If this product is > Ksp, we have a supersaturated solution If this product is < Ksp, we have an unsaturated solution If this product is = Ksp we have a saturated solution Example The solubility product for the dissociation of Mg(OH)2 is 9 x 10-12. Determine the concentration of Mg2+ and OH- at equilibrium. Solution 1. Write the equation for the reaction. Mg OH 2 Mg 2 2 OH 2. The solubility product equation is: Mg OH 2 2 9 10 12 Solution 3. If x is the number of moles of Mg2+ resulting from the dissociation, then the number of moles of OHis equal to 2x. x 2 x 9 10 12 2 4 x 9 10 3 x 1 . 3 10 12 4 2 x 2 . 6 10 moles / L Mg 4 moles / L OH .....end of example Solubility Product A B K sp x y Ksp is the solubility product for the ion pair If the concentration of either or both of the ions is increased (without a change in temperature or pressure), the product of the ionic concentration will exceed Ksp Precipitation will occur to maintain equilibrium conditions Solubility Product Precipitation can occur when a chemical reaction transforms a solute to a much less soluble form, typically mixing a precipitant with the solution Precipitation depends greatly upon pH Most metals precipitate at high pH levels as hydroxides Example Magnesium is removed from an industrial waste stream by hydroxide precipitation at a pH = 10. Determine the solubility of Mg2+ in pure water at 25° C and pKsp of 10.74. Mg OH 2 s Mg 2 2 OH Solution 1. What are your two governing equations? Mg OH 10 OH H 10 2 2 10 . 74 14 2. Two unknowns, and two equations. Solution 3. Given the pH, we know [H+]. H 10 pH 10 10 4. Solve for [OH-]2 OH OH 2 10 14 H 10 10 10 28 2 pH 14 pH 10 14 pH Solution 5. Substitute into 1st governing equation, and solve for [Mg2+]. Mg 2 10 10 10 . 74 28 2 pH 10 17 . 26 2 pH Solution 6. Substitute value of pH given in the problem statement, then convert to mg/L. NOTE: units in [ ] are moles per liter! Mg 10 2 10 24 . 3 2 . 74 mol 2 . 74 mol L L g 3 10 mol mg g 44 . 2 mg L Solution 7. For a pH of 11, the solubility is 0.442 mg/L. For a pH of 12 the solubility is 0.004 mg/L. Work these solutions on your own. ..... end of example. General Comments on Ksp Ksp is dependent on pH temperature pressure The higher the Ksp, the more soluble the compound LNAPL LNAPL saturated C.F. unsaturated Generalized Schematic: LNAPL Spill water table impermeable boundary LNAPL LNAPL water table dissolved phase transport impermeable boundary saturated C.F. unsaturated Generalized Schematic: LNAPL Spill LNAPL LNAPL water table dissolved phase transport impermeable boundary saturated C.F. residual NAPL vapor and dissolved phase transport unsaturated Generalized Schematic: LNAPL Spill water table DNAPL DNAPL impermeable boundary saturated C.F. unsaturated Generalized Schematic: DNAPL Spill water table DNAPL DNAPL impermeable boundary dissolved phase transport saturated C.F. unsaturated Generalized Schematic: DNAPL Spill C.F. residual NAPL water table DNAPL DNAPL impermeable boundary dissolved phase transport saturated vapor and dissolved phase transport unsaturated Generalized Schematic: DNAPL Spill vapor and dissolved phase transport LNAPL trapped residual NAPL water table DNAPL DNAPL impermeable boundary dissolved phase transport saturated C.F. residual NAPL unsaturated Generalized Schematic: DNAPL Spill Dissolution of NAPL NAPL may have various compounds Dissolution is a function of solubility of compound(s) groundwater velocity distribution of the NAPL pore distribution molecular diffusion of compound(s) Based on Pankow, J.F. and Cherry, J.A. 1996. Dense Chlorinated Solvents and other DNAPLs in Groundwater. Waterloo Press. Solubility Data Compound Chloroform Carbon Tetrachloride 1,1,1-Trichloroethane Trichloroethylene Source 1 8700 780 1250 1400 2 7920 793 1495 1100 3 7925 1000 720 1050 It is not uncommon to find a wide range of values for solubility across different reference. Advice: go with the most current one using a good analytical method. Solubility Data Compound Chloroform Carbon Tetrachloride 1,1,1-Trichloroethane Trichloroethylene Source 1 8700 780 1250 1400 2 7920 793 1495 1100 1. Broholm and Feenstra (1995) 23-24° C 2. Horvath (1982) 25° C 3. Mackay and Shiu (1981) 25° C 3 7925 1000 720 1050 Solubility of NAPL Mixture For an organic NAPL mixture, the aqueous phase concentration of each component that is in equilibrium with the mixture can be approximated using a solubility analog of Raoult’s Law for vapor pressure. C sat , m X m C o sat Solubility of NAPL Mixture For an organic NAPL mixture, the aqueous phase concentration of each component that is in equilibrium with the mixture can be approximated using a solubility analog of Raoult’s Law for vapor pressure. C sat , m X m C o sat Aqueous solubility of component m from the mixture, also referred to as the “effective solubility” Solubility of NAPL Mixture For an organic NAPL mixture, the aqueous phase concentration of each component that is in equilibrium with the mixture can be approximated using a solubility analog of Raoult’s Law for vapor pressure. C sat , m X m C o sat mole fraction of component m Solubility of NAPL Mixture For an organic NAPL mixture, the aqueous phase concentration of each component that is in equilibrium with the mixture can be approximated using a solubility analog of Raoult’s Law for vapor pressure. C sat , m X m C o sat solubility of the pure compound Solubility of NAPL Mixture C sat , m X m C o sat Laboratory experimental studies suggest that this equation is a reasonable approximation for mixtures of structurally similarly hydrophobic organics Other studies have shown that with most dissimilar compounds that deviations from ideal behavior are small enough to be safely ignored in environmental systems with much larger uncertainties Solubility of NAPL Mixture A comparison of observed groundwater concentrations with calculated effective solubilities values have been reported for a Pennsylvania Superfund site. DNAPL was found in numerous wells in a fractured sandstone aquifer, though at different concentrations. This type of variability is likely to be common at many multicomponent DNAPL sites. Samples from two wells are presented on the next slide for discussion. Solubility of NAPL Mixture 1 ,2,3TrichloloroProperty propane Toluene Pure compound solubility (ppm) 1 900 580 Molecular weight (g/mol) 1 46 92 Xy lene 200 1 06 Weight %, DNAPL Sample 1 Effectiv e Solubility (ppm) 23 400 4.2 35 17 43 3.8 9.1 Weight %, DNAPL Sample 2 Effectiv e Solubility (ppm) 73 1 400 0.9 8.1 5.8 16 0.9 2.3 Observ ed Groundwater Conc. Lower V alue (mg/L) Upper V alue (mg/L) 220 1 200 2.1 53 7 .3 74 1 .1 12 Note: Assumed molecular weight of unidentified portions of the samples is 150 g/mol Ethy lbenzene 1 90 1 06 Example Applied Problem Consider a liter of weathered gasoline spilled into the soil. Based on the table below, determine the effective solubilities of each compound in the water phase due to this spill. The density of the gasoline is 0.87 g/cm3. Solution Compound % of Total Grams Mass Moles Mole Fraction Benzene Toluene Ethylbenzene Xylene 30 50 15 5 3.341 4.721 1.229 0.410 0.344 0.487 0.127 0.042 261 435 130.5 43.5 Total Moles = 9.701 Solution Compound % of Total Grams Mass Moles Mole Fraction Benzene Toluene Ethylbenzene Xylene 30 50 15 5 3.341 4.721 1.229 0.410 0.344 0.487 0.127 0.042 261 435 130.5 43.5 Total Moles = 9.701 At this stage, you would use the literature to determine the solubility of each compound of BTEX and apply o C sat , m X m C sat Example Applied Problem A 37,900 L UST containing tolune has leaked and the tolune is floating at the top of the shallow aquifer as a free product. Its water solubility is controlling the concentration of tolune in the groundwater. If 37.9 x 106 L ( 10 million gallons) of groundwater have been polluted with tolune at a concentration equal to its water solubility, what volume of tolune remains as floating product? Water solubility of tolune is 546 mg/L. Density of tolune is 0.867 kg/L Solution Mass of tolune that can be dissolved based on its water solubility: = (3.79X106 L)(546 mg/L) = 2.07X1010 mg = 20,700 kg Actual mass of tolune spilled: = (37,900 L)(0.867 kg/L) = 32,900 kg Mass of tolune not dissolved in water of aquifer = 32,000 kg – 20,700 kg = 12,200 kg Therefore, volume of tolune as a free product: = (12,200 kg)/(0.867 kg/L) = 14,100 L. ..... end of example. Flammability Concern that vapors may ignite from spark or open flame if at a certain concentration Lower flammability limit, LFL Insufficient mass (conc.) is available for flame propagation Mixture is “too lean” to burn or explode Upper flammability limit, UFL Threshold concentration that limits combustion “too rich” See Table 3.8 p. 178 Flammability Limits of Mixtures Most hazardous waste disposal and storage areas contain mixtures of chemicals LFL mixture 1 n i 1 UFL mixture yi LFL i 1 n yi UFL i 1 i where yi = mole fraction of compound i n = the number of compounds in the mixtures Approach to Problem Solving Determine the v/v % of compounds Calculate the mole fraction of each compound Number of moles of each gas is directly proportional to its volume (ideal gas law) Use data to determine UFL and LFL Class Problem Determine the LFL an UFL of a gaseous mixture 1.30% benzene, 0.4% pentane and 0.6% ethanol (volume/volume). Solution Compound v/v Mole fraction LFL UFL Benzene 1.3 1.13 1.3 7.9 Pentane 0.4 0.35 1.5 7.8 Ethanol 0.6 0.52 3.3 19 Total 2.3 LFLmix 1.59 UGLmix 9.30 Spreadsheet Flash Point Definitions Flash Point: Minimum temperature at which a compound emits sufficient vapor to form an ignitable mixture with air Ignitable mixture: Vapor-air combination within flammability limits capable of propagating a flame away from the source of ignition Ignition temperature: minimum temperature required to initiate direct combustion of a material, whether it is a solid, liquid or gas Review Table 3.9 p. 183 Labels and Placards Two systems Transportation Developed by US DOT Storage Developed by National Fire Protection Association NFPA Transportation Provides critical data to first responders Placard must be placed on all four sides of the vehicle 9 Classes of hazardous materials (DOT) Use universal icons for each hazard code See p. 192 Table 3.13 Nine Classes of Haz. Mat. Used by the DOT Labels and Placards DOT hazard symbol Hazard Code 1375 Office of Hazardous Materials Safety (HAZMAT) HAZMAT Guidebook UN/NA ID # Storage Regulated by NFPA Focuses on three categories Health (for firefighting, as opposed to occupational or public health Flammability Reactivity Fire Health Each category has five levels – Table 3.15 p.197 0 No hazard 4 Severe hazard NFPA 1 4 Reactivity 2 W Hazard Class Incompatible with Water Priority Pollutants Result of a law suit filed by the Natural Resources Defense Council (NRDC) against the EPA Identification of the chemicals that would be regulated under the 1977 Amendment to the Clean Water Act See Table. 3.38 p. 203 Chemical Abstracts Service Unique classification Ambiguity is found in numerous IUPAC, common and trade names Multi-digit numbers derived from computer language description of chemical’s molecular structure Equivalent to a “social security number” for chemicals See Table 3.17 p. 200 Resources Cross Reference Index of Hazardous Chemicals, Synonyms and CAS Registry Numbers Handbook of Environmental Data on Organic Chemicals Solubility and density CRC Handbook of Chemistry and Physics Fire Protection Guide on Hazardous Materials Flash point, ignition temperature and hazardous labeling MSDS Summary of Important Points and Concepts Water solubility significantly influences environmental transport and transformation Hazardous contaminants may not mix with water (LNAPL, DNAPL) Parameters that aid in determining explosivity and flammability Flammability Range of flammable concentration in air Flash Point Temperature that results in sufficient volatilization for compound to reach lower flammability limit in the air above the liquid Ignition temperature Minimum temperature for combustion Summary of Important Points and Concepts Two label of placard systems are universal DOT and UN/NA NFPA CAS provides a definitive means of identifying hazardous chemicals Priority Pollutants identified