Workshop 1:

Assessment and Evaluation of Vapor

Intrusion at Petroleum Release Sites

BioVapor:

A 1-D Vapor Intrusion Model with Oxygen-

Limited Aerobic Biodegradation

GSI ENVIRONMENTAL INC.

Houston, Texas
www.gsi-net.com (713) 522-6300
temchugh@gsi-net.com
Vapor Intrusion Models
Types of Vapor Intrusion Models

Empirical Predictions based on observations 1000

100

from other sites (e.g., attenuation

10

(Tier 1)
1

0.1

factors). 0.01

0.001
0.1 1 10 100 1000 10000

Analytical Mathematical equation based on

(Tier 2) simplification of site conditions (e.g.,
Johnson and Ettinger).
SIMPLE MATH
Numerical models:
Others - Abreu and Johnson, Bozkurt et al.
(Tier 3) Mass flux model, foundation transport
model, etc.

Wide range of approaches to vapor intrusion

KEY modeling, varying in complexity and specificity.
POINT:
Vapor Intrusion Models
Johnson and Ettinger Model (Tier 2)
Building
RESIDENTIAL BUILDING
1 Attenuation
Due to
Exchange with
Air Ambient Air
Exchange
Advection and
Diffusion
Through
Unsaturated Unsaturated Soil
Soil
2 and Building
Foundation

Equilibrium
source Partitioning
Groundwater- area 3 Between GW and
Bearing Unit
Soil Vapor
Csv = Cgw x H

KEY Site-specific predictions based on soil type, depth to

POINT: groundwater, and building characteristics.
H = Henrys Law Constant
Vapor Intrusion Models

J&E Model: Key Assumptions

1-D Steady- Does not account for
State Model heterogeneities, preferential
pathways, or temporal
variation.
Infinite Source No mass balance; mass flux
into building can exceed
available source mass. soil

Does not account for

vapor
No biotransformation in the
Bio-
vadose zone Affected GW Plume
degradation

J&E model is generally conservative, but model

KEY
POINT: error can be very large (orders-of-magnitude).
BioVapor: 1-D VI Model w/ Bio

n Conceptual Model
n Model Inputs
n Model Outputs
n Case Studies: Example Results
Conceptual Model
What is BioVapor?

1-D Version of Johnson & Ettinger vapor

intrusion model modified to include
Analytical aerobic biodegradation (DeVaull,
Model 2007). SIMPLE MATH

Oxygen Uses iterative calculation method to

Mass account for limited availability of O2 HC
Balance oxygen in vadose zone.

Simple interface intended to

User- facilitate use by wide range of
Friendly environmental professionals.

Free, easy-to-use vapor intrusion model that

KEY accounts for oxygen-limited aerobic vapor
POINT: intrusion.
Conceptual Model
BioVapor: Conceptual Model

3 Advection, diffusion,
and dilution through
building foundation

aerobic zone 2 Diffusion & 1st order

biodegradation in
Ct aerobic zone

anaerobic zone
1 Diffusion only in
Cs anaerobic zone
Vapor Source
Conceptual Model
BioVapor: Oxygen Mass Balance
Iterative Calculation Method
Calculate oxygen demand:
- depth of aerobic zone
- HC vapor concentration
- 1st order biodegradation

??
No
anaerobic interface Increase or
O2 demand decrease depth
= supply? of aerobic zone
??

Vapor Source Yes

KEY POINT:
Final Model Calculations are
Solution cheap & quick
Conceptual Model
BioVapor: Intended Application

n Obtain improved understanding of

petroleum vapor intrusion.
n Calculate oxygen concentration/flux
YES required to support aerobic
biodegradation.
n Identify important model input
parameters and evaluate model
sensitivity.

n Predict hydrocarbon concentration in

indoor air within <10x.
NO - Site complexity
- Temporal variability
- Indoor background
BioVapor: 1-D VI Model w/ Bio

n Conceptual Model

n Model Inputs
n Model Outputs
n Case Studies: Example Results
Model Inputs
Data Requirements
Model Inputs
Environmental Factors
Model Inputs
Environmental Factors

KEY Model inputs similar to J&E, plus a few new inputs

POINT: related to oxygen-limited biodegradation:
- New inputs can be measured or estimated.
Model Inputs
Oxygen Boundary Condition

Open Soil: Constant oxygen concentration at

top of vadose zone:
(Constant - 21% oxygen in dirt crawl space
O2 Conc.) - Measured oxygen concentration 21% O2
below solid foundation Dirt Crawl Space

Solid Constant oxygen flux across top of

Foundation: vadose zone:
(Constant - Air flow from atmosphere to below
building foundation
Air Flow) Solid Foundation

Fixed User-specified depth of aerobic

zone:
Aerobic - Based on measured vertical Aerobic
Depth profile in vadose zone
- No O2 mass balance Anaerobic
Model Inputs
Forward and Backward Calculations

COC Human
Exposed Chemical
Fate & Health
Transport Dose Toxicity
Risk

x x =

START W /
COC CONC Baseline Risk Calculation RISK = ?

SSTL = ? START W /
Risk-Based Cleanup Level Calculation RISK LIMIT

COC = Chemical of Concern; SSTL = Site-Specific Target Level

Model Inputs
Backward Calculations: Conc. Vs. Risk

COC Human
Exposed Chemical
Fate & Health
Transport Dose Toxicity
Risk

x x =

OPTION 1: OPTION 2:
Calculation based Calculation based
on target indoor air on target indoor air
concentration risk limits (enter by
(from BioVapor user)
database)
Conceptual Model
Baseline Soil Respiration Rate
WHAT: Rate of oxygen
consumption in
absence of hydrocarbon
vapors (due to existing
soil bacteria)
Oxygen OPTION 1: Enter directly
concentration
OPTION 2: Estimate from soil
organic carbon

No Hydrocarbon Source Base,O2 = 1.69 x foc

(equation from, DeVaull, 2007 based on

data from several studies)

LIMITATIONS:
foc >0.02 - baseline respiration can be very high.
foc <0.001 - baseline respiration variable, but generally low.
Model Inputs
Source Type: Soil gas or Groundwater
Soil Gas: Enter VOC concentrations in
soil gas.
- Soil gas data available
- NAPL source
Groundwater: Enter VOC
concentrations in groundwater.
- Dissolved VOC plume, no NAPL
- Requires use-specified groundwater
to soil gas attenuation factor (AFGW-SG)

Software Calculation:

CSG = CGW x H x AFGW-SG

Model Inputs
Chemicals
Risk Drivers: Vadose zone
transport/oxygen demand and indoor
concentration/risk.
Other Hydrocarbons: Only vadose
zone transport/oxygen demand
- Not considered risk drivers
- No well accepted tox. values
Hydrocarbon Surrogates: Only vadose
zone transport/oxygen demand
- One surrogate can represent
multiple hydrocarbons

KEY All vapor-phase hydrocarbons must be included in

POINTS: model for proper oxygen mass balance.
Can edit chemical database and add new chemicals.
Model Inputs
Typical Vapor Composition: NAPL Source
Moderately
Fresh Weathered Weathered
Gasoline Gasoline Crude Oil

Benzene 0.25 - 1% 1-2% <0.02 0.5%

T, E, X 1 - 4% 5 - 15% <0.02 2%
Other Aromatic HCs <0.1% <1% 0.01 2%
Aliphatic HCs* 95 - 99% 85 - 90% 96 99.8%
* More than 90% of aliphatic hydrocarbons are pentane, methylated butanes and pentanes, and n-hexane.

KEY n Vapor composition can be estimated based on

POINTS: i) product type and ii) either BTEX or total TPH data.
n May need to consider methane. Source concentrations
can be in percent-range (>10,000 ppmv).
* = Value based on MCL, risk-based number would be lower.
Model Inputs
Chemicals Concentrations

Option 1: Collect source vapor

sample and analyze for
Individual individual COCs:
COCs -TO-15 w/ modified data processing
to quantify C5 & C6 aliphatics.

Option 2: Measure Source BTEX

BTEX Data Concentration: ?
- Dissolved source = mostly BTEX
- NAPL Source = estimate TPH
concentration (e.g., benzene x 100).

Option 3: For NAPL source, measure TPH

Concentration:
TPH Data - Estimate BTEX concentrations
(e.g., benzene = TPH/100)
Model Inputs
Biodegradation Rates
n Petroleum rapidly
biodegrades in
vadose zone with
oxygen

n Geometric mean first-

order rates:
- BTEX = 0.79 /hr
- Aliphatics = 71 /hr
(DeVaull, 2007)

n Biodegradation
occurs in pore water

n User can edit default

biodegradation rates
BioVapor: 1-D VI Model w/ Bio

n Conceptual Model
n Model Inputs

n Model Outputs
n Case Studies: Example Results
Model Outputs
Vapor Intrusion Risk Results
Model Outputs
Vapor Intrusion Risk Results

KEY n Model sometimes, but not always, predicts high

POINT: attenuation factors.
Model Outputs
Vapor Intrusion Risk Results

Aerobic zone

Aerobic/anaerobic
interface

Anaerobic
zone

Source
Model Outputs
Detailed Results
Model Outputs
Detailed Results: VOC Attenuation

Conclusion: For this model scenario, most VOC attenuation

occurs in aerobic zone.
Model Outputs
Detailed Results: Oxygen Demand

Conclusion: For this model scenario, most oxygen demand is

from baseline soil respiration.
BioVapor: 1-D VI Model w/ Bio

n Conceptual Model
n Model Inputs
n Model Outputs

n Case Studies: Example Results

Case Study
Case 1: Effect of Source Depth

QUESTION:
Safe distance from source to
building?

Model Inputs
n Environmental Factors:
- Residential building
(slab-on-grade) Ct Safe
- 21% O2 below slab distance?
- Dry, sandy soil
n Petroleum Source: Cs
GRO TPH Conc. = 1.5%
(40,000,000 ug/m3) Fresh Gasoline Vapor Source

Benzene Conc. =
400,000 ug/m3
(1% of TPH Conc.)
Case Study
Case 1: Effect of Source Depth
Ct Safe
distance?

QUESTION: Cs

Safe distance from source to building? Fresh Gasoline Vapor Source

1.0E+02
Benzene Concentration in

10-5 Risk Limit (3.1 ug/m3) ANSWER:

Indoor Air (ug/m3)

Model predicts sufficient

attenuation w/ 2.8 ft of
clean soil above source.
However, may need
safety factor to account
for model uncertainty
(e.g., where is top of
2.8 ft
source?)

Distance (feet)
Case Study
Case 2: Effect of Oxygen Concentration
QUESTION:
How much oxygen required
below foundation to protect
building?
Model Inputs
n Environmental Factors:
- Residential building
(slab-on-grade) Ct 10 ft
- Dry, sandy soil
- Source depth = 10 ft
n Petroleum Source: Cs
TPH Conc. = 1.5%
(40,000,000 ug/m3) Fresh Gasoline Vapor Source

Benzene Conc. =
400,000 ug/m3
(1% of TPH Conc.)
Case Study
Case 2: Effect of Oxygen
Ct 10 ft

QUESTION:
How much oxygen required below foundation to Cs

Fresh Gasoline Vapor Source

protect building?

10-5 Risk Limit (3.1 ug/m3)

Benzene Concentration in

ANSWER:
10-5 Risk Limit
Indoor Air (ug/m3)

Model predicts 2.5%

oxygen below foundation
will protect building.
(However, need may
safety factor to account
for model uncertainty.)
2.5% 2.5 %

Oxygen Concentration Below

Foundation (%)
BioVapor Model
Software and Testing

Testing Software evaluated by USEPA

contractor.

Verified accuracy of model math.

Final Available from API web site:

Software
http://www.api.org/ehs/groundwater/v
apor/index.cfm
Acknowledgements

n BioVapor Analytical Model:

George DeVaull, Shell Global Solutions
n BioVapor Software Interface:
Paul Newberry, GSI Environmental
n Project Funding, Review, Support:
API Soil and Groundwater Task Force
Harley Hopkins (now w/ Exxon) & Roger Claff
Contact Information
www.api.org/vi
Roger Claff (Claff@api.org)
(202) 682-8399