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CE 3231 - Introduction to Environmental Engineering and Science. Readings for This Class:. O hio N orthern U niversity. Chemistry, Microbiology & Material Balance. Introduction. Water & Air Pollution. Env Risk Management. Partition Coefficients and Modeling - PowerPoint PPT Presentation
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CE 3231 - Introduction to Environmental Engineering and Science
Readings for This Class:
Ohio Northern University
Introduction Chemistry, Microbiology & Material Balance Water & Air Pollution Env Risk Management
Partition Coefficients and ModelingReal data characterizing risk is difficult and expensive to come across. As thousands of chemicals enter the market place each year, models help estimate the risk based upon compound structure and physical-chemical properties. Here, we examine how partition coefficients are used to make decisions.
Exposure Assessment
pathways of exposure calculating CDI
Lecture 32Partition Coefficents and Modeling Risk
(Risk III)
Risk & Risk Assessment
Topics Covered Include: New Chemicals Review Risk Models Partitioning Coefficients
Octanol water Vapor pressure
New Chemicals Review Program
New Chemicals Review Program – Premanufacture Notice
US Environmental Protection AgencyOffice of Pollution Prevention and ToxicsToxic Substance Control Act – Section 5
Program Goal
Serve as a “gatekeeper to help manage the potential risk from chemicals new to the
marketplace.”
New Chemicals Review Program
Risk Evaluations
Risk Based - potential health risks - toxicological investigations
Exposure Based - potential exposure risks - chemical property investigations - fate modeling: ranks outcomes I to IV
New Chemicals Review Program
Physical/Chemical Properties
Estimate Concentration
in Water
Estimate Absorption
through skin, lungs and GI
Estimate Bioconcentration
Estimate Risk to Human Health and the Environment
Estimate Migration
through Soil to Groundwater
Estimate Toxicity
Boiling Point
Vapor Pressure
Estimate Concentration
in Air
Estimate Inhalation Exposure
Estimate Henry’s Law Constant
Estimate Volatilization from water
Water Solubility (estimate)
Octanol/Water Partition
Coefficient (Kow, P)
Melting Point
Estimate Removal in Wastewater Treatment
Soil/Sorption Coefficent (Koc)
(estimate)
CAS Number : 000105-55-5Chem Name : n-boulangerMol Formula: StRuCtUrEMol Weight : 186Melting Pt : -10 deg CBoiling Pt : 128 deg CWater Solubility: Value : 0.01 mg/L Temp : 37 deg C Type : EXPLog Kow (logP): Value : 3.57 Type : EXPVapor Pressure: Value : 210 mm Hg Temp : 25 deg C Type : EXPHenry's Law Constant: Value : 6.85E-004 atm-m3/mole Temp : 25 deg C Type : EST
N-boulanger is used to formulate air fresheners.
Illustrating Example
New Chemicals Review Program
Octanol/Water Partitioning
• Reported as log Kow or log P• Used to estimate water solubility, soil sediment adsorption, biological absorption (dermal, oral, GI, inhalation), bioaccumulation, and toxicity• model for partitioning within body
New Chemicals Review Program
Octanol/Water Partitioning
80% of PMN process is determined through use of log Kow
- fuels QSARs (Quantitative Structural Activity Relationships) or EPA’s ECOSAR (Ecological Structural Activity Relationship) used during the evaluation
Experimental Determination
1. Shake Flask Method
2. Slow Stir
3. Generator Column via HPLC
New Chemicals Review Program
Octanol/Water Partitioning
Non-experimental Estimation Methods
1. Fragment/segment summation
2. Correlations with molecular descriptors (shape, volume,…) with known chemistries
3. Correlations with Reversed Phase HPLC Retention Times of known chemistries
4. 3 dimensional structure
New Chemicals Review Program
The Agency prefers
experimentally derived Kow values.
Whenever non-experimental methods will be estimated, the
most conservative value will be used!
Log Kow drives partitioning between the substance and biological tissues
New Chemicals Review Program
Vapor Pressure
• rate of vapor condensation = vaporization rate of liquid• determined experimentally through automated instruments, an isoteniscope, or gas saturation procedure• strongly hints at air fraction• can be correlated for most compounds
New Chemicals Review Program
Vapor Pressure drives partitioning of compound between atmosphere.
CAS Number : 000105-55-5Chem Name : n-boulangerMol Formula: StRuCtUrEMol Weight : 186Melting Pt : -10 deg CBoiling Pt : 128 deg CWater Solubility: Value : 0.01 mg/L Temp : 37 deg C Type : EXPLog Kow: Value : 3.57 Type : EXPVapor Pressure: Value : 210 mm Hg Temp : 25 deg C Type : EXPHenry's Law Constant: Value : 6.85E-004 atm-m3/mole Temp : 25 deg C Type : EST
N-boulanger is used to formulate air fresheners.
Putting Values into Context
Aqueous Solubility Ranges
High > 500 mMmoderate 100 - 500 mMlow < 100 mM
Putting Numbers into Context
Vapor Pressure Ranges (mmHg) @ 20-30 deg F
Very highly volatile > 10-3
highly volatile 10-4 to 10-3
moderately volatile 10-5 to 10-4
low volatility 10-5 to 10-6
non volatile < 10-7
logP considered a problem when logKow > 5 (will bioaccumulate)
logP from 2 to 5 considered likely to bioaccumulate
logP from 0 to 2 potential to bioaccumulate
Henry's Constant Ranges (atm m3/mol)
non volatile < 3x10-7
low volatility 3x10-7 to 1x10-5
moderate volatility 1x10-5 to 1x10-3
high volatility > 1x10-3
CAS Number : 000105-55-5Chem Name : n-boulangerMol Formula: StRuCtUrEMol Weight : 186Melting Pt : -60 deg CBoiling Pt : 128 deg CWater Solubility: Value : 0.01 mg/L Temp : 37 deg C Type : EXPLog Kow: Value : 3.57 Type : EXPVapor Pressure: Value : 210 mm Hg Temp : 25 deg C Type : EXPHenry's Law Constant: Value : 6.85E-004 atm-m3/mole Temp : 25 deg C Type : EST
Putting Values into Context
Aqueous Solubility Ranges
High > 500 mMmoderate 100 - 500 mMlow < 100 mM
CAS Number : 000105-55-5Chem Name : n-boulangerMol Formula: StRuCtUrEMol Weight : 186Melting Pt : -60 deg CBoiling Pt : 128 deg CWater Solubility: Value : 0.01 mg/L Temp : 37 deg C Type : EXPLog Kow: Value : 3.57 Type : EXPVapor Pressure: Value : 210 mm Hg Temp : 25 deg C Type : EXPHenry's Law Constant: Value : 6.85E-004 atm-m3/mole Temp : 25 deg C Type : EST
Putting Values into Context
logKow considered a problem when logKow > 5 (will bioaccumulate)
logKow from 2 to 5 considered likely to bioaccumulate
logKow from 0 to 2 potential to bioaccumulate
CAS Number : 000105-55-5Chem Name : n-boulangerMol Formula: StRuCtUrEMol Weight : 186Melting Pt : -60 deg CBoiling Pt : 128 deg CWater Solubility: Value : 0.01 mg/L Temp : 37 deg C Type : EXPLog Kow: Value : 3.57 Type : EXPVapor Pressure: Value : 210 mm Hg Temp : 25 deg C Type : EXPHenry's Law Constant: Value : 6.85E-004 atm-m3/mole Temp : 25 deg C Type : EST
Putting Values into Context
Vapor Pressure Ranges (mmHg) @ 20-30 deg F
Very highly volatile > 10-3
highly volatile 10-4 to 10-3
moderately volatile 10-5 to 10-4
low volatility 10-5 to 10-6
non volatile < 10-7
CAS Number : 000105-55-5Chem Name : n-boulangerMol Formula: StRuCtUrEMol Weight : 186Melting Pt : -60 deg CBoiling Pt : 128 deg CWater Solubility: Value : 0.01 mg/L Temp : 37 deg C Type : EXPLog Kow: Value : 3.57 Type : EXPVapor Pressure: Value : 210 mm Hg Temp : 25 deg C Type : EXPHenry's Law Constant: Value : 6.85E-004 atm-m3/mole Temp : 25 deg C Type : EST
Putting Values into Context
Henry's Constant Ranges (atm m3/mol)
non volatile < 3x10-7
low volatility 3x10-7 to 1x10-5
moderate volatility 1x10-5 to 1x10-3
high volatility > 1x10-3
CAS Number : 000105-55-5Chem Name : n-boulangerMol Formula: StRuCtUrEMol Weight : 186Melting Pt : -60 deg C LIQUIDBoiling Pt : 128 deg CWater Solubility: Value : 0.01 mg/L LOW SOLUBILITY Temp : 37 deg C Type : EXPLog Kow: Value : 3.57 LIKELY TO BIOACCUMULATE Type : EXPVapor Pressure: Value : 210 mm Hg VERY HIGHLY VOLATILE Temp : 25 deg C Type : EXPHenry's Law Constant: Value : 6.85E-004 atm-m3/mole Temp : 25 deg C MODERATELY VOLATILE Type : EST
Putting Values into Context
Fate considers reactions too!
1. Biologically mediated degradation
2. Hydrolysis
3. Photolysis (direct or indirect)
New Chemicals Review Program
All the models EPA uses to determine reactions are based upon the physical/chemical parameters reported in the PMN
Aqueous Solubility Ranges
High > 500 mMmoderate 100 - 500 mMlow < 100 mM
Putting Numbers into Context
Vapor Pressure Ranges (mmHg) @ 20-30 deg F
Very highly volatile > 10-3
highly volatile 10-4 to 10-3
moderately volatile 10-5 to 10-4
low volatility 10-5 to 10-6
non volatile < 10-7
logP considered a problem when logKow > 5 (will bioaccumulate)
logP from 2 to 5 considered likely to bioaccumulate
logP from 0 to 2 potential to bioaccumulate
Henry's Constant Ranges (atm m3/mol)
non volatile < 3x10-7
low volatility 3x10-7 to 1x10-5
moderate volatility 1x10-5 to 1x10-3
high volatility > 1x10-3
New Chemicals Process
1. Gatekeeper for new chemicals
2. Dependent upon partitioning
3. Physical/chemical properties key
4. Modeling approach
New Chemicals Review Program
“…we’re busy alright. I can send you home with about 500 submissions right now. Do you have a U-Haul?...”