Final Exam for ES8901 29 points total

December 7, 2020

The final exam is a take-home test. It should be completed by December 14 and submitted
through D2L. Under the “Assessments” tab, and the “Assignments” folder, you will find a “Final
Exam” sub-folder. Dec 14 is a soft deadline. I would ask that if you need additional time, please
contact me to discuss.

In completing the exam, you are encouraged to consult your book, your notes, the previous
assignments and answer keys, the videos posted to the course D2L shell. You may also consult
internet sources, if you wish. You may not consult any other person (apart from asking me
questions).

For the final exam, we are going again consider one single scenario.

Benzene (image below) is a petroleum hydrocarbon and is commonly distilled for use as an
organic solvent in a wide variety of industrial applications. Its molecular formula is C 6H6, and
you will notice three carbon-carbon double bonds in the ring structure.

Benzene has the following physical properties:

Molecular weight: 78.11 g mol-1
Density: 0.88 g cm-3
Solubility: 1780 mg L-1
Vapour pressure: 0.125 atm
Log KOW: 2.13

You have become used to me imagining bad things happening. So, you will not be disappointed
that we will imagine a tank storing benzene at a refinery has a catastrophic leak. The benzene
forms a pool on the ground. Containment berms are compromised, and some benzene will
permeate soil. You will notice that benzene has some, but relatively low, solubility. You will also
notice that benzene is fairly (not highly, but fairly) volatile, so some will also evaporate into the
gas phase.
Name: Anastazia Jagdeo
Student: 500637954

Part 1: Sub-surface
OK, let’s first think about the benzene migrating into the soil. The upper stratum of soil is
referred to as the vadose zone.
1. What is the Vadose Zone? (1 point)
- Looking at a subsurface environment, the saturated and unsaturated zones are usually
porous and granular mineral material. The upper portion of the unsaturated is also
called the Vadose Zone, where both air and water are present in the pore spaces
between mineral grains. The water that is not lost through evaporation occurs as a thin
film on the grains surface and in the interstices between. This does not completely fill
the pores spaces, as air fills the remaining balance of the pore space.

2. How will the relative humidity (the moisture content) of soil in the vadose zone affect
the rate at which benzene migrates though the vadose zone? (1 point)
- The vadose zone holds a low moisture content which causes the rate of which benzene
mitigation to be affected. Considering a soil with a constant porosity in the unsaturated
zone, due to the low moisture content, water will move more slowly throughout the
soil. Looking specifically at benzene, if the capacity of the soil is dry, the lower the
hydraulic conductivity becomes. The hydrogen bonds that are found within benzene will
draw more water from the soil and as the soil becomes drier, it will cause disruptions
within the flow of the contaminant resulting in the speed of its migration to be much
slower as it moves through the zone.

After the benzene migrates through the vadose zone, it reaches the saturated zone (aquifer).
3. When the benzene reaches the saturated zone, will it mix with water, form a LNAPL
layer, or sink and form a DNAPL layer? Explain? (1 point)
- Benzene is a petroleum - based solvent which when released into the soil can percolate
towards the water table. Due to benzene being less dense than water, it will mix with
the water and form a LNAPL layer that will remain at the surface of the water table.

4. Now that it is in the subsurface environment, I want you to consider what you might
do if you were asked to outline a strategy to manage this problem.
a. What are some remediation strategies that you might consider? Would you
expect more efficient biological degradation under aerobic or anaerobic
conditions (consider its molecular structure)? What are two things you might do
to enhance biological degradation? What is the feasibility of photolysis? Of
hydrolysis? (5 points)
- Remediation Strategies for removing LNAPL can be done by using a well and either
pumping methods; Water-NAPL separator (using water/NAPL pump) or NAPL phase by a
second pump (water pump and NAPL pump).
 - It is expected that more efficient biological degradation is seen under aerobic conditions
due to the molecular structure of benzene which consists of hydrogen and carbon
molecules creating what is known as petroleum hydrocarbons. Aerobic conditions
favour the biodegrading of petroleum hydrocarbons.
- Two methods that might be used to enhance biological degradation is the injection of
oxygen containing compounds such as (H2O2, ORC) or the injection of organic substrate
(lactate, molasses, soy).
- The likelihood for photolysis to occur is dependent on if the molecule has a double bond
and/or rings as they tend to absorb energy from photons. Also, photolysis can work for
contaminants on the surface of soil.
- The likelihood for hydrolysis to occur is dependent on the pH conditions and the
absence of light or microbial activity. This process is more feasible towards esters, ester
derivatives or alkyl halides.

b. What is some possible containment and/or extraction strategies you might

consider? (3 points)
- Chemical Oxidation can be used as a possible containment extraction strategy that
utilized oxidizing reagents (catalyzed sodium persulfate, Fenton’s Reagent) to reduce
the high concentrations of the containment. This strategy is typically coupled with a
treatability study to recommend the appropriate reagent dosage. This is very site and
contaminant specific.
- Permeable Reactive Barriers can be also used as a possible extraction strategy that relies
on the groundwater flow to move the contaminant towards the reactive media. The
permeable barrier will allow the water to pass through but will retard the contaminant
using either a physical (filter) chemical (oxide) or biological process to remove the
contaminant.
- Air Sparge/Soil Vapor Extraction is another extraction strategy that using vertical sparge
wells that are injected with air into the water table to remove VOC out of the
groundwater. The air is then vented out and treated.

Now that the benzene is in the saturated zone, we need to consider the movement of the
benzene plume, because as the plume spreads, it becomes harder to contain and treat.
5. What might we best hope for in terms of the nature of porous material (e.g. are we
hoping the saturated zone is gravelly, sandy, or clayey? Are we hoping for well-sorted
or poorly sorted material? What is our best-case scenario for the plume being
contained)? (1 point)
- The best hope in terms of the nature of the porous material in the saturated zone would
be clay that is poorly sorted - to limit the movement of plume from spreading faster.
- The best scenario for the plume to be contained is to have a low porous material, with
high organic material present and low hydraulic conductivity to keep the plume from
moving and allowing for clean-up to be easier.
 6. Would we expect hydraulic conductivity to be greater in the horizontal or vertical
plane? In other words, would we expect the plume of benzene to move faster
horizontally or with depth? Why? (2 points)
- The hydraulic conductivity is expected to be greater in the horizontal plane. It is
expected that the plume of benzene to move faster horizontally because of the
anisotropy found within porous materials. Each material is typical flat shape and long in
orientation. Therefore, when benzene flows through, it will move easily in a lateral
direction while in the vertical motion may take longer as benzene would have to move
along the long axis of the material.

Suppose that, based on your recommendations, a decision is made to extract the benzene from
the aquifer by installing a well, pumping the water and benzene to the surface, and separating
the benzene (let’s assume then that the pressure to remediate the site, to contain the spill, and
the resources to do so align). A well is installed at the centre of this spill, in the area where we
would expect the maximum concentration of benzene in the aquifer.

One of the most pressing concerns with this spill is the presence of a well that is used by a
water hauler. This water hauler has a permit to extract water, and to deliver the water to rural
homes with cisterns. So, it is critical that the benzene plume not reach this well. The distance
between well 1 (the well installed to extract the benzene) and well 2 (the well that is used by
the water hauler) is 1.5 km. The hydraulic conductivity of the porous material in the aquifer is
7.5 x 10-3 cm s-1.

7. If the hydraulic head in well 1 is 27 m and in well 2 is 16 m, what is the specific

discharge of the aquifer (qw) (discharge toward well 2)? (1 point) [Note: this is the
movement of water toward well 2 before we start pumping from the extraction well]

Qw = K x dh/dx
-3 -1
K = 7.5 x 10 cm s
dh = 1500 m
dx= 27m-16m = 11m

Qw = (7.5 x 10-3 cm s-1) x (11m/1500m)

Qw = 5.5 x 10-5 cm s-1

Therefore, the specific discharge of the aquifer is 5.5 x 10 -5 cm s-1.

Now, suppose that the well for extracting benzene has been installed quickly. By the time the
well has been installed, the plume has dispersed no more than 90 m in radius. To be
conservative, we are going to assume that 100 m radius from the well represents the
containment area, and all benzene is within this containment cylinder. With the well installed,
you (and your team) begin pumping to extract benzene. You extract water at a rate of 0.3 m -3 s-1
( = Qw). The average depth of the aquifer is 17 m. Again, the hydraulic conductivity is 7.5 x 10-3
cm s-1 (or 7.5 x 10-5 m s-1). We assume from a precipitation / rainfall model that the radius of
effect is 150 m (R = 150 m).
8. What will be the drawdown (s) of the aquifer at a distance of 100 m from the well (r =
100 m)? (2 points)

s = (Qw/2πKb) x ln (R/r)
Qw = 0.3 m-3 s-1
K = 7.5 x 10-5 m s-1
R= 150m
R= 100m
Depth = 17m

s = (0.3 m-3 s-1/ 2π x 7.5 x 10-5 m s-1 x 17m) x ln (150m/100m)

s = (0.3 m-3 s-1 / 8.01 x 10-3 m2s-1) x 0.405 m/m
s = 15.2 m

Therefore, the drawdown(s) of the aquifer at the distance of 100m from the well is 15.2m

9. Given that the difference in hydraulic head between well 1 and well 2 was 11 m (see
question 7), and given the draw-down of the aquifer at the outer boundary of the
containment area (see your answer to question 8), will benzene-laden water continue
to flow toward well 2? (1 point)

- Based from the results calculated in question 7 and 8. The benzene – laden water will
not continue to flow towards well 2 because as the rate if Qw increases, so does the
drawdown of the aquifer. As the drawdown (q8) from the well is 15.2m, meaning that
the water table is being pulled down 15.2m at steady state when withdrawing 7.5 x 10-3
cm s-1 of water. Due to the withdrawal of water from the well, it reduces the hydraulic
head from 11m.
Now, let’s assume a different scenario. In this scenario, your proposal for an extraction well
went unheeded. A decision is delayed, and in the meantime the plume does continue to spread.
You now want to determine how fast the plume will advance in the aquifer toward well 2.
Suppose that the organic content of the porous medium is 0.8%, the porosity of the aquifer
material is 0.19, and the bulk density is 2.0 g cm-3.
10. Use a relationship for aromatics of: Log KOC = 0.937 log KOW – 0.006. Determine Kd (1
point)
logKoc = 0.937 log Kow – 0.006

Log Koc = (0.937)(2.13) – 0.006

Log Koc = 1.990
Koc = 101.990
Koc = 97.7 mLg-1

Kd = 0.008 x Koc
Kd = 0.008 x 97.7 mL g-1
Kd = 0.7816

Therefore, the Kd is 0.7816.

11. Given this value of Kd (from Q10) determine the retardation factor (R). (1 point)

R = 1 + (0.7816 mL g-1 x 2 g cm-3) / 0.19 = 9.23 mL g-1

Therefore, the retardation factor (R) is 9.23 mL g-1

12. Using specific discharge calculated above (qw, determined in Q7), determine the
velocity (v) of water movement through the aquifer, and from this, determine the rate
of advancement of the benzene plume (v/r). (1 point)
Qw = 5.5 x 10-5 cm s-1

Velocity (v) = q/n

v = 5.5 x 10-5 cm s-1 / 0.19
v = 2.9 x 10-4 cm s-1

v/R = 2.9 x 10-4 cm s-1 / 9.23

v/R = 3.14 x 10-5 cm s-1
 13. Given the rate of advance of this plume (3.14 x 10-7 m s-1 ) , and given the distance
between the spill site and the well (1500 m), approximately how many years would it
take for the benzene to reach well 2 if we do absolutely nothing in terms of
remediation? (1 point)
(advance rate) = 3.14 x 10-5 cm s-1 = 3.14 x 10-7 m s-1

1500 m = 4,777,070,064 seconds

-7 -1
3.14 x 10 m s

4,777,070,064 seconds x 1 year = 151.38 years

31556952 seconds

Therefore, it would take benzene 151.38 years to reach well 2 if nothing in terms of
remediations were done.

14. Finally, given that well 2 is the most urgent concern in terms of source protection, and
given a conservative degradation rate of 0.05 y-1 (5% degradation per year) for the
benzene in the subsurface environment, is the “do nothing” approach reasonable? (1
point)

- Yes. Doing nothing is a reasonable action because with a 0.05 y -1 conservation

degradation rate for the benzene in the subsurface environment, it will take 7.57 years
until benzene will be completely degraded before it reaches well 2.

Part 2: Atmosphere

Now, let’s think about the benzene that volatilized. The refinery is in an industrial area, and let’s
suppose that there is substantial particulate matter in the air arising from incomplete
combustion. Because these particles arise from incomplete combustion, they have higher
organic content (3%). Some of the benzene that is in the atmosphere will absorb into the
organic phase of the particulate matter. This is a bit of an extension of what we talked about in
class, so I will guide you a bit. Concentration of benzene in particulate matter = concentration
of benzene in air * Kd, or:
Cp = C a * K d
 15. You already calculated KOC in response to Q10. You then calculated Kd in the context of
the organic content of porous material in the aquifer. Now, use your previous value of
KOC, and the percent organic content of particulate matter in air to calculate a new
value of Kd. (1 point)

Koc = 97.7 mLg-1

Kd = 0.03 x Koc
Kd = 0.03 x 97.7 mL g-1
Kd = 2.931

Therefore, the Kd of particulate matter in air is 2.931.

The concentration of benzene in the air over the spill site is 15 mg L-1. Each 1 L of air has a mass
of 1.2 g. So, concentration of benzene can be expressed as 0.0125 g benzene / g air.
16. Given your value of Kd (from Q15), calculate Cp (in units of g benzene / g particulate
matter). (1 point)

Kd = 2.931 Cp = Ca * Kd
Ca = 0.0125 g benzene/ g air Cp = (0.0125 g benzene/ g air) (2.931)
CP = 0.0366 g benzene/ g particulate matter

17. The concentration of particulate matter in the air is 10 mg L-1. Calculate the amount
(mg) of benzene absorbed to particulate matter in one L of air by multiplying the
concentration of benzene per gram of particulate matter by the amount of particulate
matter per L of air. (1 point)

Ca = 10 mg L-1

Amount (mg) of benzene absorbed to particulate matter in 1L of air = 0.0366 g benzene/ g

particulate matter x 10 mg L-1 x 1L = 0.366 mg

18. The particulate matter containing absorbed benzene will eventually settle. If the
depositional velocity of the particulate matter is 0.25 cm s-1, calculate the dry
depositional rate (dry flux, or J) of absorbed benzene in units of g m -2 d-1. (1 point)

J = Vd x Ca J = (0.25 cm s-1) x 0.0125 g benzene/g air

J = (0.0025m s-1) x (0.0125 g benzene/g air) x (86400s/day)
J = 2.7 g m-2 d-1
19. Think about degradation processes we discussed in Chapter 3. What process do you
think is most likely to account for this degradation? What about the molecule would
facilitate this mode of degradation? (2 points).

- Photolysis can be used to most likely account for this degradation. Due to the molecular
structure of benzene – which holds a double-bonds between the carbon structures,
photolysis is most likely to be effective.
- In situ enhanced biodegradation can also be used to enhance this biodegradation, as it is
enhanced through the addition of carbon bond/sources. This aerobic condition can
favor the biodegradation of petroleum hydrocarbons more effectively.