5 Partitioning, Sorption, and Exchange at

Surfaces

5.1. Describe the three mechanisms of sorption.

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5.2. Describe the contaminant and sorbent characteristics that influence sorption.

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5.3. What is the difference between a soil particle size and a textural class?

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5.4. Explain the differences between primary and secondary minerals. Provide examples of
each.

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5.5. Using Figure 5.2, provide the soil textural class for each of the following particle size
distributions.
a. 20% sand, 30% silt, 50% clay
b. 88% sand, 6% silt, 6% clay
c. 48% sand, 23% silt, 21% clay
d. 63% sand, 32% silt, 5% clay
e. 30% sand, 17% silt, 53% clay

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5.6. Analysis of a sandy loam soil found that the total metals concentrations on the soil are 88
mg/kg Na+, 42 mg/kg K+, 110 mg/kg Ca2+, and 21 mg/kg Al3+. Determine the cation
exchange capacity of the soil.

SOLUTION

Convert all concentrations to meq/100 g:

Sodium:
mg 1 mmole 1 meq 3.82 meq 0.382 meq
88 × × = =
kg 23.0 mg mmole kg 100 g
Potassium:
mg 1 mmole 1 meq 1.07 meq 0.107 meq
42 × × = =
kg 39.1 mg mmole kg 100 g
Calcium:
mg 1 mmole 2 meq 5.49 meq 0.549 meq
110 × × = =
kg 40.1 mg mmole kg 100 g
Aluminum:
mg 1 mmole 3 meq 2.33 meq 0.233 meq
21 × × = =
kg 27.0 mg mmole kg 100 g

0.382 meq 0.107 meq 0.549 meq 0.233 meq

CEC = ∑ all cations = + + +
100 g 100 g 100 g 100 g

Answer:
𝟏. 𝟐𝟕 meq
=
100 g

5.7. The regression equation

log S = –1.37 log Kow + 7.37

was derived to estimate Kow from water solubility (S, in µmoles/L). Using the water
solubility data of Table 3.3 for benzene, anthracene, and 2,4,6-trichlorophenol, use this
equation to calculate Kow. Compare the calculated values with the experimental values of
Table 5.7.

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SOLUTION

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5.8. A Langmuir isotherm analysis was conducted, and the results show that the slope = 5.8 and
the y-intercept = 2.2. From these results, determine a and b for the Langmuir equation.

SOLUTION

Linear analysis of the Langmuir equation results in a slope = 1/a and y-intercept = 1/(a·b).
Slope = 5.8 = 1/a; therefore, a = 0.172
y-intercept = 2.2 = 1/(a·b) = 1/(0.172b); therefore, b = 2.64.
Answer: a = 0.172 and b = 2.64

5.9. A soil evaluated for cabaryl sorption has been found to follow the Langmuir isotherm
with a = 10.4 mg/kg and b = 2.5. A remediation team proposed adding 5,000 kg (11,000
lb) of the soil to a 50,000-L (13,210-gal) pond as an emergency response measure against
a spill. The initial carbaryl concentration after the spill is 11 mg/L. Determine the
equilibrium carbaryl concentration after sorption. If the concentration after sorption is
complete needs to be 5 mg/L, will the proposed process be effective?

SOLUTION

a = 10.4 mg/kg, b = 2.5

Determine the mass of carbaryl sorbed:
x = (C0 – Ce) (mg/L)·V (L)
x = (11 – Ce) mg/L·50,000 L = (550,000 – 50,000·Ce) mg
m = 5,000 kg

Substitute the information into the Langmuir isotherm:

𝑥 𝑎𝑏𝐶𝑒
𝐶𝑠 = =
𝑚 1 + 𝑏𝐶𝑒
550,000 − 50,000 · 𝐶𝑒 (10.4)(2.5) · 𝐶𝑒
𝐶𝑠 = =
5,000 kg 1 + (2.5 · 𝐶𝑒 )

𝐶𝑒 = 9.0 mg/L

The process would not be successful because the Ce of 9.0 mg/L is greater than 5.0 mg/L

5.10. Batch isotherm analysis of a soil has shown that sorption of dimethyl phthalate follows the
Freundlich isotherm with n = 0.556 and KF = 3.69. If 1800 L (476 gal) of a 43 mg/L solution

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 of dimethyl phthalate floods a 400-m3 (523-yd3) section of soil with a bulk density of 1800
kg/m3, what will its equilibrium concentration be?

SOLUTION
𝑥
Freundlich: 𝐶𝑠 = 𝑚 = 𝐾F 𝐶𝑒 1/𝑛
n = 0.556
KF = 3.69
Find mass of contaminant sorbed:
x = [(43 – Ce) mg/L](1,800 L) = (77,400 – 1,800Ce) mg

Find mass of soil:

m = (400 m3)(1,800 kg/m3) = 720,000 kg

Determine equilibrium concentration from Freundlich isotherm:

(77,400 − 1,800Ce) mg 𝑚𝑔 1/0.556
𝐶𝑠 = = 3.69 · 𝐶𝑒
720,000 kg 𝑘𝑔

Using an equation solver, or by trial and error:

𝑪𝒆 = 𝟎. 𝟏𝟒 mg/L

5.11. A dry well receives 2000 L (528 gal) of aqueous waste containing 25 mg/L MIBK, which
sorbs to the soil in a manner characterized by the Langmuir isotherm with a = 8.50 mg/kg
and b = 0.66. The dry well is 1.5 m (4.9 ft) in diameter, and the soil has a bulk density of
2100 kg/m3. If the mean equilibrium concentration of the MIBK in the soil is 0.5 mg/L,
how deep will the MIBK sorption be?

SOLUTION
𝑥 𝑎𝑏𝐶𝑒
Langmuir: 𝐶𝑠 = =
𝑚 1+𝑏𝐶𝑒

a = 8.50 mg/kg
b = 0.66
x = (original contaminant mass) – (mass in water at equilibrium)
x = (25 mg/L)(2,000 L) – (0.5 mg/L)(50,000 L) = 25,000 mg
Expression for the mass of soil per depth z:
Diameter = 1.5 m; r = 0.75 m

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 Volume = πr2·z = 1.77·z (units = m3)
m = (1.77· z m3)(2,100 kg/ m3) = 3,720·z kg

Substitute the information into the Langmuir isotherm:

𝑥 𝑎𝑏𝐶𝑒
𝐶𝑠 = =
𝑚 1 + 𝑏𝐶𝑒
mg
25,000 mg (8.50 kg ) (0.66)(0.5)
𝐶𝑠 = =
3,720 · 𝑧 kg 1 + (0.66)(0.5)

𝒛 = 𝟑. 𝟐 m

5.12. An isotherm analysis was performed on a surface soil and an aqueous solution of toluene.
Six 1-L beakers were used, each containing 1.0 g of soil and varying concentrations of
toluene. After allowing the system to equilibrate for 24 hours, analysis of the aqueous phase
showed the following results:

Initial Aqueous Toluene Aqueous Toluene

Concentration (mg/L) Concentration after Sorption (mg/L)
215 112
180 87.6
140 48.5
114 4.8
86 2.5
48 1.8

Fit the data to Langmuir and Freundlich isotherms. Determine the empirical coefficients
for the isotherm equation which best fits the data.

SOLUTION

1. Arrange the data to find Ce/Cs and to generate a Langmuir plot:

x = (C0 – Ce) (mg/L)·V (L)

Cs = x/m (mg/kg)

m C0 Ce V x (mg sorbed) Cs (mg/kg) Ce/Cs (kg/L) Ce/Cs (mg/L)

(kg soil) (mg/L) (mg/L) (L) = x/m
0.001 215 112 1.0 103 103,000 0.00109 1090
0.001 180 87.6 1.0 92.4 92,400 0.000948 948
0.001 140 48.5 1.0 91.5 91,500 0.000530 530
0.001 114 4.8 1.0 109.2 109,200 0.0000440 44.0

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 0.001 86 2.5 1.0 83.5 83,500 0.0000299 29.9
0.001 48 1.8 1.0 46.2 46,200 0.0000390 39.0

y = 10.0 x + 16.3 R2 = 0.99

2. Convert the data to the ln of Cs and Ce to generate data for a Freundlich plot:

ln Ce ln Cs
4.72 11.5
4.47 11.4
3.88 11.4
1.57 11.6
0.92 11.3
0.59 10.7

y = 0.0930 x + 11.1 R2 = 0.30

Based on an R2 = 0.99, the Langmuir isotherm is the best fit. Determine a and b:
Slope = 10.0 = l/a, a = 0.10 mg/kg
y-intercept = 16.3 = 1/(a·b) = 1/(0.1b), b = 0.613

5.13. Using a groundwater contaminated with 74 mg/L dichromate, an isotherm analysis was
performed using 500-mL aliquots and varying concentrations of subsurface solids. The
groundwater was allowed to equilibrate with the sorbent, and the aqueous phase was
analyzed for residual dichromate. The following aqueous phase concentrations were found:

Subsurface Solids Concentration (g) Aqueous Dichromate Concentration after

Sorption (mg/L)
2 54.3
4 39.8
6 26.5
8 18.1
9 10.7
10 5.9

Fit these data to the Langmuir and Freundlich isotherms and determine the empirical
constants for the best fit isotherm.

SOLUTION

1. Arrange the data to find Ce/Cs and to generate a Langmuir plot:

x = (C0 – Ce) (mg/L)·V (L)

Cs = x/m (mg/kg)

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 m C0 Ce V x (mg sorbed) Cs (mg/kg) Ce/Cs (mg/L)
(kg soil) (mg/L) (mg/L) (L) = x/m
0.002 74.0 54.3 0.5 9.85 4925 11000
0.004 74.0 39.8 0.5 17.1 4275 9310
0.006 74.0 26.5 0.5 23.8 3967 6680
0.008 74.0 18.1 0.5 28.0 3500 5170
0.009 74.0 10.7 0.5 31.7 3520 3040
0.010 74.0 5.9 0.5 34.1 3400 1730

y = 192 x + 1180 R2 = 0.98

2. Convert the data to the ln of Cs and Ce to generate data for a Freundlich plot:

ln Ce ln Cs
3.99 8.50
3.68 8.36
3.25 8.29
2.90 8.16
2.37 8.16
1.77 8.13

y = 0.159 x + 7.79 R2 = 0.83

Based on an R2 = 0.98, the Langmuir isotherm is the best fit. Determine a and b:
Slope = 192 = l/a, a = 0.00521 mg/kg
y-intercept = 1180 = 1/(a·b) = 1/(0.00521b), b = 0.0163

5.14. What are the assumptions and limitations of using Kd as a basis for sorption?

SOLUTION

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5.15. To determine the soil distribution coefficient (Kd), 10 g of dry soil is spiked with 100 mg
of ring-labeled 14C-atrazine, 10 mL of deionized water is added, and the system is shaken
for 24 h. The aqueous and solid phases are separated, and the solid phase is extracted with
50 mL of methylene chloride while the aqueous phase is extracted with three successive 5-
mL portions of methylene chloride. The atrazine concentration in the 50 mL of soil extract
is 10 mg/L, and the concentration in the combined 15 mL from the aqueous extractions is
0.4 mg/L. Based on this information, calculate Kd.

SOLUTION

5.16. Describe how the soil distribution coefficient, Kd, has been developed from the Freundlich
isotherm.

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5.17. Describe the relationship between Kd, Koc, soil organic matter, and why Kow can be used as
a predictor of adsorption.

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5.18. A Freundlich plot developed from well cuttings was performed for the solvent MIBK. The
slope in the linear portion was equal to 410. At low MIBK concentrations (in the linear
region of the Freundlich curve), what percentage of the MIBK is in the aqueous phase?

SOLUTION

5.19. A Freundlich plot developed from well cuttings was performed for the herbicide
chlorosulfuron. The slope in the linear portion was equal to 34.
a. At low chlorosulfuron concentrations (in the linear region of the Freundlich curve),
what percentage of the chlorosulfuron is in the aqueous phase?
b. What are Kd and Koc for chlorosulfuron in this system? The organic carbon content of
the well cuttings is 0.15%.

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SOLUTION

5.20. The following data have been collected for batch isotherm analysis of
hexachlorocyclopentadiene in well cuttings from a contaminated groundwater system.
Volume of aqueous solution used: 500 mL
Mass of well cuttings: 5 g
Organic carbon content of well cuttings: 2%

C0 (mg/L) Ce (mg/L)
0.4 0.02
1.8 0.04
3.7 0.05
5.1 0.1
7.6 1.2
9.2 3.8
11.0 4.9
12.4 5.3

Based on these data, estimate Kd and Koc for the groundwater system.

SOLUTION

x = (C0 – Ce) (mg/L)·V (L)

Cs = x/m (mg/kg)

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 m C0 Ce V x (mg sorbed) Cs (mg/kg)
(kg soil (mg/L) (mg/L) (L) = x/m
cutting)
0.005 0.40 0.02 0.5 0.39 78
0.005 1.8 0.04 0.5 0.88 176
0.005 3.7 0.05 0.5 1.83 366
0.005 5.1 0.1 0.5 2.50 500
0.005 7.6 1.2 0.5 3.20 640
0.005 9.2 3.8 0.5 2.70 540
0.005 11.0 4.9 0.5 3.05 610
0.005 12.4 5.3 0.5 3.55 710

Plot Cs vs Ce:

Linear portion of
sorption curve

Run linear regression on first four data points:

y = 5210 x +6.55
slope = Kd = Cs/Ce = 5210 L/kg = 5210 mL/g
Kd = Koc·foc = 5210/0.2
Kd = 2.61  105

5.21. Using tables, find the Kow for

a. 4,6-Dinitro-o-cresol
b. DDT
c. TCE
d. PCE
e. Hexachlorobenzene
f. Naphthalene
g. 1,1,1-Trichloroethane

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SOLUTION

5.22. If the surface area of a soil is 42 m2/g, determine the minimum soil organic carbon content
at which the SOC is the primary sorbent for
a. Toluene
b. Naphthalene
c. TCA
d. Endrin
e. Di-n-octyl phthalate

SOLUTION

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5.23. A soil with organic carbon content of 2% is contaminated with p-xylene. Estimate the Kd
for p-xylene in the soil using the appropriate regression equation from Table 5.9. The soil
Sa is 24 m2/g.

SOLUTION

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5.24. A soil with organic carbon content of 0.75% and Sa of 16 m2/g is contaminated with
chrysene. Estimate the Kd for chrysene in the soil using the appropriate regression equation
from Table 5.9.

SOLUTION

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5.25. A soil with organic carbon content of 4% and Sa of 12 m2/g is contaminated with 2,4-
dinitrotoluene. Estimate the Kd for 2,4-dinitrotoluene in the soil using the appropriate
regression equation from Table 5.9.

SOLUTION

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5.26. A soil with organic carbon content of 3.5% is contaminated with carbofuran. Estimate the
Kd for carbofuran in the soil using the appropriate regression equation from Table 5.9. The
soil Sa is 24 m2/g.

SOLUTION

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5.27. A soil with organic carbon content of 0.3% is contaminated with Aroclor 1242. Estimate
the Kd for Aroclor 1242 in the soil using the appropriate regression equation from Table
5.9.

SOLUTION

5.28. The following empirical relationship has been developed for PAHs:

log Koc = 14,300·S + 0.27

where S = water solubility in moles/L. For the PAH naphthalene, determine the Kd in a
groundwater system with organic carbon content of 0.046%. Assume that organic carbon
is the primary sorbent.

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SOLUTION

5.29. Determine Kd for the following compounds in a soil with 0.48% organic carbon. Assume
that organic carbon is the primary sorbent.
a. Benzene
b. TCE
c. PCE
d. Anthracene
e. Pyrene
f. DDT
g. Pentachlorophenol

SOLUTION

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5.30. Repeat Problem 5.29, but calculate Kd for a soil with 4% organic carbon.

SOLUTION

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5.31. A soil profile contains organic carbon in the following concentrations.
A horizon (0–15 cm): 3.6% organic carbon
B horizon (15–50 cm): 1.2% organic carbon
C horizon (50–100 cm): 0.8% organic carbon
Subsurface: 0.3% organic carbon |
Estimate the diuron Kd for each of the horizons of the soil profile. Assume that
organic carbon is the primary sorbent in all of the soil horizons.

SOLUTION

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5.32. For a surface soil with an organic carbon content of 1.6%, estimate Kd for benzene,
chlorobenzene, 1,4-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3,5-tetrachlorobenzene,
pentachlorobenzene, and hexachlorobenzene. What can be concluded about the effect of
chlorination on Kd? Assume that the soil organic carbon is the primary sorbent.

SOLUTION

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5.33. Determine the soil distribution coefficient for perchloroethylene as a function of soil
organic carbon from 0.2% to 2.0% at 0.2% intervals and plot the results. What can be
concluded about the effect of soil organic carbon on the soil distribution coefficient?

SOLUTION

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5.34. Polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins usually remain in the top
1 meter of soil when disposed of or spilled onto soil. Explain this phenomenon based on
soil and contaminant characteristics.

SOLUTION

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5.35. A transformer ruptured 10 years ago, releasing Aroclor 1260 onto the soil. Assuming
degradation is negligible, at what depth in the soil profile would you expect to find the
PCBs?

SOLUTION

5.36. Spillage of organochlorine and organophosphate insecticides occurred at a pesticide rinse

and formulation area. Which class of chemicals would migrate faster through the soil?

SOLUTION

5.37. Based on the data of Appendix G, what conclusion(s) can you draw between PAH ring size
and Kow? What is the effect of chlorination on Kow?

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5.38. A groundwater with a pH of 7.5 containing acetone and trichloroacetic acid is to be treated.
Granular activated carbon has been proposed to sorb the contaminants. Do you agree with
this proposal? Why or why not?

SOLUTION

5.39. Of gasoline, diesel, and motor oil, which would you expect to migrate the fastest in soils
and groundwater? Which would be the slowest? Justify your answer using Kow.

SOLUTION

5.40. Determine the retardation factor for

a. MEK
b. Naphthalene
c. Hexachlorobenzene
for a soil-water system in which the bulk density = 1.8 g/cm3, the porosity = 0.36, and the
soil organic carbon content = 2.0%.

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SOLUTION

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5.41. Repeat Problem 5.40 using a soil organic carbon content of 0.05%. Assume that the soil
organic carbon is the primary sorbent.

SOLUTION

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5.42. Using vinyl chloride (low Kow) and hexachlorobenzene (high Kow), and the two organic
carbon contents of the soils (2.0% and 0.05%), make a quantitative judgment of which
variable (Kow or foc) asserts the greatest influence on the retardation factor.

SOLUTION

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5.43. Using the retardation factor, estimate the time for DDT to reach a well 2 km (1.24 miles)
away if the pore-water velocity = 0.1 m/day, the soil bulk density = 1.2 g/cm3, n = 0.45,
and the average soil organic carbon content = 0.01%. Assume that soil organic carbon is
the primary sorbent and that degradation and dispersion are negligible.

SOLUTION

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5.44. A groundwater contaminated with 16 mg/L nickel also contains 240 mg/L suspended solids
and 8.1 mg/L total organic carbon. The pore-water velocity is 55 cm/day, and the
subsurface solids consist of 60% sand, 20% clay, and 1.4% free iron oxides. Based on the
information given, develop a plot of nickel concentration as a function of time at a depth
of 5 m (16.4 ft).

SOLUTION

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 be

5.45. A groundwater system contains 10 mg/L Zn, and the pore-water velocity is 30 cm/day. The
waste also contains 1200 mg/L suspended solids and 110 mg/L total organic carbon. The
aquifer solids consist of 80% sand, 10% silt, and 2% free iron oxides. Using the procedure
of Amoozegar-Fard et al., determine the time required for the aquifer solution of 1 mg/L
to reach a well 1000 m (0.6 miles) downgradient.

SOLUTION

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5.46. A landfill leachate that has migrated to groundwater contains 5 mg/L Cd, 300 mg/L total
organic carbon, and 550 mg/L suspended solids. The aquifer solids consist of 60% sand,
20% clay, and 1.5% free iron oxides. The pore-water velocity is 12 cm/day. How long will
it take for a 3 mg/L concentration of Cd to reach a well 200 m (656 ft) away?

SOLUTION

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5.47. Read the comprehensive description of sorption provided by Weber et al. (1991). Write a
two-page summary of the mechanistic models used to describe sorption.

SOLUTION

The summary is open ended and its content will vary.

5.48. Review the article written by Amoozegar-Fard et al. (1984). Propose how you would
design a laboratory study to quantify the migration rate of lead at a specific hazardous
waste site.

SOLUTION

The summary is open ended and its content will vary.

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