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Air and Noise Pollution (DC) (ESC 504)

I SEM - M. TECH Department Core Course (2019–20 MONSOON SEM)

ASSIGNMENT SOLUTION-1 (August 2019) Total marks: 41

Topics Covered:
• Atmospheric chemistry:
• Physical and chemical characteristics of atmosphere
• Evolution of atmosphere
• Mixing ratio

Topic 1: Physical and chemical characteristics of atmosphere Marks: 5

Question 1.1. Answer the following questions in brief: Marks: 1 X 5


a. Which is the fundamental difference between the troposphere and the stratosphere,
making them regarded as different parts of the atmosphere?
b. Is vertical motion most common in the troposphere or the stratosphere? Why?
c. The global average height of the tropopause is 14 km. Calculate the pressure at that
altitude, assuming constant atmospheric temperature of 250 K.
d. Assume that the global air flow from the troposphere to the stratosphere is equal to
the opposite flow (from the stratosphere to the troposphere), being 5.9 1017 kg/year
in each of the two directions. Calculate the residence times of air in the troposphere
and the stratosphere. The pressure at the stratopause is 1 hPa.
e. Explain why the residence times of stratospheric and tropospheric air differ.
Solution:
a. The temperature change with altitude. Troposphere: temperature decrease with altitude;
Stratosphere: temperature increase with altitude
b. The troposphere, because the temperature increase with altitude in the stratosphere
(inversion) induces a strong counteracting force against vertical motion => very stable
conditions
c. The vertical pressure profile can be obtained from the barometric law: p(z) = p0 exp(-z/H),
where H = RT/(Mag), p0 = the average pressure at the surface (984 hPa), z = the altitude,
R = the gas constant, T = the temperature, Ma = average atmospheric molar mass and g =
the gravity. p(14 km) = 145 hPa.
d. The pressure at any given layer is caused by the weight of the overlying air: pA = mg =>
m =pA/g. The mass of the troposphere is given by the mass of the atmosphere minus the
mass of the air above the tropopause: mT = (p0 – ptp)A/g = (98400 – 14500)4π(6.37
106)2/9.81 = 4.36 1018 kg and for the stratosphere mS = (ptp – psp)A/g = 7.48 1017 kg
Residence times: τT = mT/Fout = 4.36 1018 / 5.9 1017 = 7.4 years; τS = 1.3 years
e. The mass of the troposphere is much larger than the stratosphere and the mass flows in
both directions are equal. Therefore, more time is needed to exchange the tropospheric air.
Topic 2: Evolution of atmosphere Marks: 12

Question 2.1. Answer the following questions in brief: Marks: 1 X 6


a. Figure 1 shows the pre-industrial geochemical cycle of carbon. Calculate the
residence time of carbon in the atmosphere from Figure 1.
b. Form a combined ocean reservoir of the surface, middle and deep ocean reservoirs.
Calculate the residence time of carbon in the new ocean reservoir.
c. You find the carbon mass in the pre-industrial atmosphere in Figure 1. Calculate
the pre-industrial concentration of CO2 in the atmosphere as a mixing ratio,
assuming that all carbon in the atmosphere is in the form CO2 and that CO2 is well
mixed in the entire atmosphere.
d. Discuss the validity of the two assumptions made in question 1c.
e. Figure 2 shows how the CO2 concentration has changed over the years at Mauna
Loa, which can be assumed to be representative for global concentrations. Estimate
the carbon mass in the atmosphere of today, making the same assumptions as in
question 1c. Assume that we have first order (i.e. proportional) sink processes, and
estimate the size of the sinks for atmospheric carbon.
f. Increased atmospheric CO2 concentration increases the carbon transport to the
biosphere and the ocean. Briefly discuss the long-term capability of these to
reservoirs to act as sinks for increasing atmospheric CO2 concentrations.

Figure 1. The pre-industrial geochemical cycle of carbon. Figure 2. The CO2 concentration
The masses of carbon in the reservoirs are given in in the air at Mauna Loa, Hawaii.
Pg (1015 g) and the exchange in Pg per year.
Solution:
a. The residence time is given by  = m/Fout; where m is the mass in the reservoir and Fout are
the sum of sinks:  = 615/(60 + 60) = 5.1 years.
b. All flows between ocean reservoirs becomes internal in the combined ocean reservoir, and
the new reservoir contains the sum of the masses of the three original reservoirs:
 = m/Fout = (26,000 + 9,700 + 840)/(60 + 0.2) = 607 years.
c. Average molar mass of air: Ma = 0.78 mN2 + 0.21 mO2 + 0.01 mAr = 28.97 kg/kmole Mass
of the atmosphere: mag = pA; ma = 4R2p/g = 4*(6.37 106)2*98400/9.81 = 5.12 1018 kg
Mixing ratio C = nCO2/na = (mC/MC)/(ma/Ma) = [note that the mass of carbon (mC not mCO2)
is given in Fig.] = (615 1012/12.01)/(5.12 1018/28.97) = 2.91 10-4 = 291 ppmv
d. CO2 is the most common carbon-containing gas in the atmosphere because it is the final
stable oxidation product of the oxidation ongoing in the atmosphere. As a result of the
chemical stability of CO2 the residence time is long. As a result, CO2 is well mixed in the
atmosphere.
e. From Fig. C = 401 ppmv; 𝑚𝑐 = 𝑛𝐶 𝑀𝐶 = 𝐶 𝑛𝑎 𝑀𝐶 = 𝐶 𝑚𝑎 𝑀𝐶 = 𝐶 𝑚𝑎 𝑀𝐶 /𝑀𝑎 =
401 10−6 𝑥 5.12 1018 𝑥 12.01
= 849 𝑃𝑔 carbon First order sink processes:
28.97
Fout = km; Pre-industrial: k = m/Fout = 615/(60 +60) =166 Pg/year
f. Biosphere: In order to preserve the loss rate constant of the biosphere the Net Primary
Productivity (NPP) must increase proportionally to the atmospheric increase. There are
some results pointing to increased growth-rate with increasing CO2 concentration, but that
concentration is not the only limiting factor for the growth. In addition, land use, e.g.
deforestation in the tropics, has a large impact on the NPP. Oceans: Increased CO2
concentration in the air increases the dissolution and concentration of compounds
originating in CO2. This causes acidification of the oceans, which shifts the air-sea
equilibrium towards increased fraction of CO2 in the atmosphere implying that the loss-
rate constant decreases. Greenhouse gases also induces warming which could enhance or
decrease NPP and that would lower the dissolution in the oceans.
Question 2.2 Fill in the blanks Marks: 0.5 X 12
a. The early Earth was a highly volcanic place due to energy released in its interior by
__________________ and __________________.
b. Compared to the Earth atmosphere, Venus atmosphere are _______________ whereas,
Mars atmosphere are ______________.
c. The first atmosphere was formed by outgassing of gases trapped in the interior of the early
earth. Name those outgasses which was in abundance at early phase of Earth
____________, ______________ and _____________
d. The biological era of earth atmosphere was marked by the simultaneous decrease in
_________________ and the increase in _______________.
e. The evolution of atmosphere is divided into four different stages. Other than biological era,
the three different stages are ____________, _________________ and ______________.
Solution:
a. Radioactive decay and gravitational accretion.
b. Thicker and Thinner
c. H2O, CO2, N2 and Sulfur gases
d. Atmospheric CO2 and Oxygen O2
e. Origin, Pre-biological and Microbial.

Topic 3: Mixing ratio Marks: 24

Question 3.1. During aerosol characterization experiments covering a globally representative


range of natural and anthropogenically perturbed environments atmospheric concentrations of
dimethyl sulfide (DMS) between 250 and 500 ng m-3 were determined. Convert this range of
concentration (in (pptv) at sea level and 298 K. (2 Marks)
Solution:
A part per trillion by volume (pptv) is:
1 𝑣𝑜𝑙𝑢𝑚𝑒 𝑝𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡 1 𝐿 𝑝𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡 1 𝑛𝐿 𝑝𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡
Pptv = = =
1012 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑖𝑟 1012 𝐿 𝑜𝑓 𝑎𝑖𝑟 𝑚3 𝑜𝑓 𝑎𝑖𝑟

Assuming that Ideal Gas Law (PV =nRT) is accurate under these conditions (298 K and 1 atm),
one mole of a gas would occupy:
𝑅𝑇
Vm =
𝑃

Where, P = Pressure, V = Volume, n = mole, R = gas constant, T = temperature


𝐿
0.082 𝑎𝑡𝑚 𝑥 298 𝐾
𝑚𝑜𝑙 𝐾
Vm = = 24.44 L
1 𝑎𝑡𝑚

The molecular weight of dimethyl sulfide (DMS) is 62 g mol-1. Thus, atmospheric concentrations
of DMS between 250 and 500 ng m-3 equal to:
𝑛𝑔 𝐷𝑀𝑆 1𝑔 1 𝑚𝑜𝑙 𝐷𝑀𝑆 24.44 𝐿 109 𝑛𝐿 98.5 𝑛𝐿 𝐷𝑀𝑆
250 x 109 𝑛𝑔 x x x = = 985 ppt
𝑚3 62 𝑔 1 𝑚𝑜𝑙 1𝐿 𝑚3

𝑛𝑔 𝐷𝑀𝑆 1𝑔 1 𝑚𝑜𝑙 𝐷𝑀𝑆 24.44 𝐿 109 𝑛𝐿 98.5 𝑛𝐿 𝐷𝑀𝑆


500 x 109 𝑛𝑔 x x x = = 197.5 ppt
𝑚3 62 𝑔 1 𝑚𝑜𝑙 1𝐿 𝑚3

Question 3.2. There are 92 people in a public establishment of 16x12x2.5 meters. Of these, half
are smokers and, on average they smoke 2 cigarettes per hour. One of the many toxic chemicals
present in tobacco cigarettes is formaldehyde (methanal). Each cigarette, when smoked, releases
1.4 mg of formaldehyde. When this toxic compound is present in the air at levels at or above 0.05
ppm, it can lead to acute physical symptoms such as watery eyes, burning sensations in the eyes
and other irritating effects. Assume that 10% (volume) of the formaldehyde escapes through
opened windows and doors and that 60% (volume) of the formaldehyde retained inside the
building is oxidized to CO2. The ambient temperature and the pressure in the establishment are
25°C and 100.66 kPa, respectively. (2+2 Marks)
a. Determine whether after an hour of exposure to tobacco smoke, individuals present in the
establishment are likely to feel irritating effects.
b. Calculate the concentration of CO2 (in ppmv) resulting from the oxidation of the
formaldehyde in the air.
Solution:
There are 92 people in a public establishment, of these, half are smokers and, on average they
smoke 2 cigarettes per hour and that each cigarette, when smoked, releases 1.4 mg of
formaldehyde, we get:
2 𝑐𝑖𝑔𝑎𝑟𝑟𝑒𝑡𝑒𝑠 1.4 𝑚𝑔 𝐻𝐶𝐻𝑂 1 𝑚𝑔 90 𝑔 1 𝑚𝑜𝑙 0.039 𝑚𝑜𝑙 𝐻𝐶𝐻𝑂
46 smokers x x x 103 𝑚𝑔 x 100 𝑔 x 30 𝑔 𝐻𝐶𝐻𝑂 =
ℎ 𝑐𝑖𝑔𝑎𝑟𝑟𝑒𝑡𝑒 ℎ

The ambient temperature and the pressure in the establishment are 25°C and 100.66 kPa,
respectively. assuming that Ideal Gas Law (PV = nRT) is accurate under these conditions, 0.0039
mol of formaldehyde at 298.15 K at 100.66 kPa would apply:
𝐿
0.0039 𝑚𝑜𝑙 𝐻𝐶𝐻𝑂 𝑥 0.082 𝑎𝑡𝑚 𝑥 298.15 𝐾
𝑚𝑜𝑙 𝐾
V= 𝑎𝑡𝑚 = 0.09452 L HCHO
100.66 𝑘𝑃𝑎 𝑥 1
101.3 𝑘𝑃𝑎

The volume of the 16 x 12 x 2.5 meters establishment is 480 m3.


A part per million by volume (ppmv) is:
1 𝑉𝑜𝑙𝑢𝑚𝑒 𝑝𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡 1 𝐿 𝑝𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡 1 𝑚𝐿 𝑝𝑜𝑙𝑙𝑢𝑡𝑎𝑛𝑡
ppmv = = =
106 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑖𝑟 106 𝐿 𝑜𝑓 𝑎𝑖𝑟 𝑚3 𝑜𝑓 𝑎𝑖𝑟

Therefore, the concentration of formaldehyde in units of parts per million is:


0.094 𝐿 𝐻𝐶𝐻𝑂 1000 𝑚𝐿
𝑥 = 0.197 ppmv HCHO
480 𝑚3 1𝐿

When this toxic compound is present in the air at levels at or above 0.05 ppmv, it can lead to acute
physical symptoms such as watery eyes, burning sensations in the eyes and other irritating effects.
Assuming that 10% (volume) of the formaldehyde escapes through opened windows and doors
and that 60% (volume) of the formaldehyde retained inside the building is oxidized to CO2, the
real concentration of formaldehyde is 0.0787 ppmv, which is above 0.05 ppmv.
40 𝑝𝑝𝑚𝑣 𝐻𝐶𝐻𝑂 𝑛𝑜𝑡 𝑜𝑥𝑖𝑑𝑎𝑡𝑒𝑑
0.197 𝑝𝑝𝑚𝑣 𝐻𝐶𝐻𝑂 = 0.0787 ppmv HCHO
100 𝑝𝑝𝑚𝑣 𝐻𝐶𝐻𝑂

And, the concentration of CO resulting from the oxidation of the formaldehyde in the air is:
40 𝑝𝑝𝑚𝑣 𝑜𝑥𝑖𝑑𝑎𝑡𝑒𝑑 𝑡𝑜 𝐶𝑂2
0.197 𝑝𝑝𝑚𝑣 𝐻𝐶𝐻𝑂 = 0.1182 ppmv CO2
100 𝑝𝑝𝑚𝑣 𝐻𝐶𝐻𝑂
Question 3.3. State whether each of the following statement about concepts of Air Pollution and
the Characteristics of the Atmosphere is True (T) or False (F) and why (0.5 X 8 Marks)
1 The residence time is the time it takes for 25% of the quantity of a pollutant to disappear
in its various sinks
2 Greenhouse gases absorb and reemit visible radiation, whereas they are transparent to
infrared radiation
3 At 25 °C and 1 atmosphere, 5 ppm of carbon monoxide equal 5714 µg m-3
4 Tropospheric ozone absorbs most of the biologically damaging UV sunlight
5 Atmospheric pressure decreases exponentially with increasing altitude
6 Thermosphere is of interest to aerospace engineers because it is traversed by commercial
airplanes
7 Precursors can be primary pollutants or natural constituents of the atmosphere
8 Acid rain is a local air pollution problem

Solution:
1. False:
The residence time is the time it takes for 50% of the quantity of a pollutant to disappear
in its various sinks. This time depends on the atmospheric pollutant sources and sinks as
well as its reactivity.
2. False:
Greenhouse gases absorb and reemit infrared radiation, whereas they are transparent to
most of the solar radiation. They are so called because their presence limits the heat
escaping into space, much like the glass of a greenhouse, thus building up the temperature
of the atmosphere.
3. True:
Assuming that it behaves as an ideal gas, at 25º (C and 1 atmosphere, 5 parts per million
of carbon monoxide equal 5714 µg·(m-3)
4. False:
Stratospheric ozone absorbs most of the biologically damaging UV sunlight. In contrast,
the tropospheric or the ground-level ozone is an air pollutant that damages human health,
vegetation, and many common materials. It is a key ingredient of urban smog.
5. True:
Atmospheric pressure decreases exponentially with increasing altitude, from an average of
1013 mb at the Earth’s surface to 140 mb at 14 km.
6. False:
Stratosphere is of interest to aerospace engineers because it is traversed by commercial
airplanes, whereas thermosphere is of interest to space scientist because it must be
traversed by space vehicles en route to or from the moon or the planets.
7. True:
Precursors can be primary pollutants or natural constituents of the atmosphere such as
water vapor or solar radiation. Nitric oxide (NO) is a precursor molecule to nitrogen
dioxide (NO2); NO2 absorbs sunlight and initiates atmospheric photochemical reactions.
8. False:
Acid rain is a regional-continental air pollution problem caused by emissions of sulfur
dioxide and nitrogen oxide.
Question 3.4. Anthropogenic carbon dioxide emissions into the atmosphere amounted to 178 Gt
from Jan. 1990 to Dec. 1997. Calculate the fraction of this emitted carbon dioxide that remained
in the air, given that in that same eight-year period, the carbon dioxide concentration in air rose by
11.1 ppm. Note that the molar masses of C, O, and air, respectively, are 12.0, 16.0, and 29.0 g,
that the mass of the atmosphere is 5.1 x 1021 g, and that 1 Gt is 1015 g. (2 Marks)
Solution:
Mass gain in CO2 = (mole gain in CO2) (44.0 g/mol)
where mole gain in CO2 = (11.1/106) (5.1 x 1021 g air) / (29.0 g mol-1) = 1.95 x 1015 mol
Mass gain in CO2 = (1.95 x 1015 mol) (44.0 g/mol) = (8.59 x 1016 g) (1 Gt/1015 g) = 85.9 Gt
% left in atmosphere = 85.9*100/178 = 48%

Question 3.5. The average concentration of PCBs in the atmosphere around the Great Lakes is
about 2 ng/m3. What is this concentration in molecules/cm3? The average molecular weight of
PCBs is 320. (2 Marks)

Solution:

2 𝑛𝑔 𝑚𝑜𝑙 𝑔 6.022 𝑥 1023 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑚3


C = ( 𝑚3 ) (320 𝑔) (109 𝑛𝑔) ( ) (106 𝑐𝑚3) = 3.8 x 106 molecules cm-3
𝑚𝑜𝑙

Question 3.6. Calculate the mixing ratio of O3 at the peak of the O3 layer (z = 25 km; P = 35 hPa;
T = 220 K). Would this mixing ratio be in violation of the EPA air quality standard if it were found
in surface air? (2 Marks)

Solution:
At the peak of the ozone layer, nO3 = 5 x 1012 molecules cm-3. The density of air at the altitude is

𝐴𝑣 𝑃 6.022𝑥1023 𝑥 35𝑥102
Na = = = 1.2 x1024 molecules m-3 = 1.2x1018 molecules cm-3
𝑅𝑇 8.31 𝑥 220

𝑛𝑂3
And the corresponding O3 mixing ratio is CO3 = = 4.2 ppmv = 4200 ppbv. This is fifty time the
𝑛𝑎
O3 air quality standard for surface air.

Question 3.7. Calculate the mixing ratio of O3 in surface air (z = 0 km; P = 1000 hPa; T = 300 K).
Is it in compliance with the EPA air quality standard? Notice that the relative decrease in mixing
ratio between 25 km and the surface is considerably larger than the relative decrease in number
density. Why is this? (2 Marks)

Solution:

In surface air, nO3 = 1x1012 molecules cm-3. The density of air at that altitude is

𝐴𝑉 𝑃 6.022𝑥1023 𝑥 1000𝑥102
na = = = 2.4 x 1025 molecules m-3 = 2.4 x 1019 molecules cm-3
𝑅𝑇 8.31 𝑥 300

and the corresponding O3 mixing ratio CO3 = nO3/na = 42 ppbv, which is in compliance with the O3
air quality standard. The relative decrease of CO3 from 25 to 0 km is much larger than the relative
decrease of nO3 because of the change in atmosphere pressure:

(Z )
CO 3( Z2 ) nO 3( Z2 ) na ( Z2 ) nO 3( Z2 ) pz1T 2 nO 3( Z2 )
= x = x = 0.048 x between o to 25 km.
CO 3( Z 1) nO 3( Z2 ) na ( Z2 ) nO 3( Z2 ) pz2 T ( Z1 ) nO 3( Z1 )

Question 3.8. The density of air 20.0 km above Earth's surface is 98.3 g/m3. The pressure of the
atmosphere is 43.7 mm Hg and the temperature is -66.3 °C. What is the average molar mass of the
atmosphere at this altitude? (2 Marks)
Solution:
Number of moles of air in 1 L:
43.7
𝑛 𝑛 𝑃 ( )𝑎𝑡𝑚
760
= 1 𝐿 = 𝑅𝑇 = = 3.388 x 10-3 mol L-1
𝑉 0.08205 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙−1 𝐾−1 𝑥 (273.15−66.3) 𝐾

1 𝑚3
Density: 98.3 g m-3 x 1000 𝐿 = 98.3 x 10-3 g L-1

98.3 𝑥 10−3 𝑔 𝐿−1


Average molar mass: 3.388 𝑥 10−3 𝑚𝑜𝑙 𝐿−1 = 29.01 g mol-1.
Question 3.9. Our lecture hall holds a maximum of 250 students. A ventilation rate of 8.88 l/s per
student must be maintained to avoid build-up of CO2. Determine the residence time of air in the
lecture hall in minutes, assuming that that the lecture hall has a volume of 2150.11 m3. (2 Marks)
Solution:
𝑴 𝟐𝟏𝟓𝟎.𝟏𝟏 𝒎𝟑 𝒙 𝟏𝟎𝟎𝟎 𝑳 𝒎−𝟑
τ= = = 968.5 s = 16.14 min.
𝑭 𝟐𝟓𝟎 𝒙 𝟖.𝟖𝟖 𝑳 𝑺−𝟏

Question 3.10. A one-compartment home of volume 400 m3 has an infiltration rate of 0.3 air
changes per hour with its doors and windows closed. During an episode of photochemical smog,
the outdoor concentration of PAN is 75 ppb. If the family remains indoors, and the initial
concentration of PAN inside is 9 ppb, how long will it be before the PAN concentration inside
rises to 40 ppb? (2 Marks)
Solution:

C = Cmax (1 – exp(-kt))
(40-9) = (75-9) (1- exp(-0.3t)
31
(66 − 1) = -0.530 = -exp(-0.3t)

ln(0.530) = -0.3t
t = 2.1 hr