Black Carbon (BC) Concentrations in Selected Air Pollutant Sources

Julius Ceasar C. Deocareza1, Diana V. Montecastro2

1
Nuclear Analytical Techniques and Application Section
Philippine Nuclear Research Institute
Commonwealth Avenue, Diliman, Quezon City, 1101 Metro Manila, THE PHILIPPINES
________________________________________________________________________

1. Introduction

One of the most serious environmental concerns in urban areas is air pollution

especially in view of the harmful health effects that have been associated with ambient fine

particles. Emissions from motor vehicles and biomass burning, lead from battery

reprocessing, and paint pigment production are all transported as fine particles particularly

in urban areas. According to Puja Mondal, there have been two classifications of air

pollutants: particulate and gaseous. Particulate substances include solid and liquid particles

while gaseous include substances that are in the gaseous state at normal temperature and

pressure.

Particulate matter (PM) are solid and liquid particles in air that may contain soot,

smoke, metals, dust and water. These particles vary in size, shape and density. PM is

typically described in terms of its size and is directly linked to its potential in causing health

problems. Aerodynamic equivalent diameter (AED) is a term that refers to the diameter of

a unit density sphere that would have the identical settling velocity as the particle

(NARSTO, 2004). Coarse particulate matter otherwise known as PM10 has an AED ranging

from 2.5 to 10 µm. Fine particulate matter (PM2.5) has an AED less than 2.5 µm. PM2.5 pose

the greatest problem because of its ability to bypass the body’s defenses and can easily get
into the lungs and bloodstream. Two carbonaceous constituents are found in PM: the

organic carbon (OC) and elemental carbon (EC). OC are unstable and volatile while EC

are non-volatile and can be measured.

Black Carbon (BC), categorized under PM10, are carbonaceous materials emitted by

both naturally occurring and anthropogenic soot. BC are produced through incomplete

combustion of organic materials such as fossil fuel, biofuel and residues from biomass

burning. BC is closely associated with elemental carbon (EC) and both absorbs light in the

visible range. Though both are nearly the same, unlike BC, EC cannot be reduced to CO2

when heated to 800°C. EC and BC are measured by thermal and optical techniques

respectively.

Black carbon emissions in the atmosphere has a long life of days in urban areas and

could possibly be transported over long distance from its sources. Vehicles fueled by diesel

are the leading contributors for BC emissions.

This study aims to estimate the black carbon concentration from vehicular emissions

loaded with different fuels, biomass burning, tire pyrolysis by measuring the reflectance of

aerosol filters exposed from these sources using EEL Smoke Stain Reflectometer and to

determine the amount of concentration of particulate matter from the selected sources.

2. Review of Related Literature

A study conducted by Gabriel State et. al., entitled as “Identification of Air Pollution

Elements in Lichens used as Bioindicators, by the XRF and AAS Methods” aimed to

identify the air pollutants in Targoviste using lichens as bioindicators. Targoviste engages
in social-economical activities such as production of steel, stainless steel, energy in power

stations, oil exploitations and traffic. Lichen arises from algae and cyanobacteria and had

been advantageous because of its long-life span and exposure with atmosphere. Results

showed that Fe, Zn and Pb has the highest concentration in air due to the steel factories

operating in Targoviste. The study also concluded that AAS, though much slower and

destructive, provided a more precise quantitative analysis of every element than XRF.

Table 1.

Another study entitled “Multi-element Analysis and Characterization of Atmospheric

Particulate Pollution in Dhaka”, conducted by Bilkis A. Begum et.al. used PIXE (proton

Induced X-Ray Emission) and PIGE (Proton Induced Gamma Ray Emission) to measure

over 20 elements present in atmospheric particle sample. The study aimed to identify

fingerprints of various particulate matter and assess their impact especially on health.
 Results showed that motor vehicle’s fingerprint included a high load of black carbon

and sulfur with a little of silicon and aluminum.

Table 2. Motor vehicle’s fingerprint

Sea salt fingerprint of course has high loading of sodium and chlorine and bromine in

coarse fractions; fine fractions included sodium and chlorine.

Table 3. Sea salt fingerprint

Two-stroke engine fingerprint included a high loading of black carbon, zinc,

manganese and copper for fine fractions and zinc and bromine for coarse fractions.
Table 4. Two-stroke engine fingerprint

3. Methodology

3.1. Preparation of Filters

A total of 23 pairs of coarse (8 μm pore size) and fine C0.4 μm pore size) Nuclepore

polycarbonate filters were transferred into their individual containers and set aside in a

desiccator prior to weighing using Mettler MT5 micro analytical balance. One pair of filter

was set aside to serve as the blank.

The pre-weighed filters were then transferred in a single filter cassette as shown in

figure 1. Through this set-up, particles of PM 2.5-10 will be suspended in the coarse filter

while particles of PM 2.5 will be suspended in the fine filter

 Figure 1. Gent sampler head containing the filter cassette

3.2 . Sample Collection

3.2.1. Sample Collection from Vehicular Emissions

A total of total of 16 vehicles were used. Out of these 16 vehicles, 5 were taxis, 3 were

motorcycle, and 8 were privately-owned car. The taxis are all have manual transmissions

in which 3 were fueled by unleaded gasoline, 1 by premium gasoline and 1 by LPG. The

motorcycle all have 4 stroke engines in which 2 were fueled by premium gasoline and 1

unleaded gasoline. The privately-owned car all have manual transmissions in which 3 were

fueled by special fuel, 3 by diesel, 1 by unleaded gasoline and 1 by premium gasoline.

Gent sampler was utilized for the collection of vehicular emissions. Improvised set-up

from a previous study consisting of a plastic tube with both ends attached directly from the

vehicle exhaust and collection head of the Gent sampler was adopted. The vehicle engine

was set to revolve for 1 minute to saturate the plastic tube with vehicular exhaust before

proceeding to the sample collection proper for 5 minutes. Exposed filters were weighed
accordingly.

Figure 2. Improvised set-up for sample collection

3.2.2. Sample Collection from Biomass Burning

The sample used for biomass burning were mix of dried leaves and twigs. The

leaves and the twigs were ignited at the same time using a Bic lighter in a 1 feet hole dug

in the soil. The smoke from the fire were saturated using a plastic tube for 1 minute. The

Gent sampler was initiated for 2.5 minutes for sample collection. The used filters were then

weighed.

3.2.3. Sample Collection from Tire Pyrolysis

TWI 2.75-17-41B-45, a tire used for motorcyles, was used for tire pyrolysis.

Ethanol was sprayed on to serve as a fuel to burn the tire. Before saturating the smoke in

the plastic tube, the tire was left to burn for 2 minutes to eliminate the traces of ethanol.

Smoke were collected for 1 minute to saturate the plastic tube and the Gent sampler was
initiated for 2.5 minutes. The exposed filters were weighed and then stored in the

desiccator.

3.4. Determination of the Concentration of Particulate Mass

Using the readings from flow meter of the Gent sampler, the total volume of air

consumed was determined by subtracting the initial reading from the final reading. The

amount of particulate mass suspended in the filter was determined by subtracting the initial

weight from the final weight. The equation used to determine the PM concentration is:

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑃𝑀, 𝑚𝑔
𝐹𝑖𝑙𝑡𝑒𝑟 𝐿𝑜𝑎𝑑 =
𝑇𝑜𝑡𝑎𝑙 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐴𝑖𝑟, 𝑚3

3.5. Estimation of Black Carbon Concentration

The reflectance of the exposed filters was determined using EEL Smoke Stain

Reflectometer following the procedure of in the operating instruction. The BC

concentration was obtained using the formulas:

1 𝑅𝑜
𝐵𝐶𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝜀ln( )
2 𝑅

𝐵𝐶 = [(𝐵𝐶𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑆𝑎𝑚𝑝𝑙𝑒) − (𝐵𝐶𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝐵𝑙𝑎𝑛𝑘) × 12.57 𝑐𝑚2 /𝑚3

Where BCinitial is the black carbon with a unit of mass per area

Ro is the reflectance in percentage with the value of 100

 R is the reflectance in percentage of the exposed filter.

BC is the black carbon concentration with a unit of mass per volume

Preparation of Preparation of Collection of

Filters Set-up Sample

Determination
Estimation of
of the
Black Carbon
Concentration of
Concentration
Particulate Mass

Figure 3. Summary of Methodology

4. Results and Discussion

Exposed filters from tire pyrolysis showed darker shade of black-color stain followed

by diesel fuel cars. Filters exposed from biomass burning showed yellowish color. Color

stain in biomass burning may vary depending on the physical characteristics of the material.

Filters exposed from Unleaded gasoline, premium gasoline, Shell V-power nitro plus and

LPG showed lighter shade of stain.

 Table 5. Fine Load, reflectance and BC concentration

Black
Sample Fine Load Carbon
Code Source (ng/m3) R% (ng/m3)
FB1 Biomass Burning 7027778 88.23 10910
FB2 Biomass Burning 36954545 76.27 23996
FB3 Biomass Burning 2254902 74.33 26302
FT1 Tire Pyrolysis 10388889 2.80 320704
FT2 Tire Pyrolysis 53646341 5.40 261734
FT3 Tire Pyrolysis 7976190 8.57 220300
FP1 Premium 5540000 40.13 81641
FP2 Premium 1485714 88.20 10944
FU1 Unleaded 3541096 87.23 11933
FS1 Shell V-power 859649 89.47 9664
FS2 Shell V-power 517857 89.17 9965
FS3 Shell V-power 695652 89.30 9831
FD1 Diesel 5484375 39.47 83145
FD2 Diesel 5878788 28.07 113751
FD3 Diesel 12388889 15.60 166483
FP3 Premium 614943 71.23 30126
FP4 Premium 3000000 46.63 68164
FU2 Unleaded 4087500 59.47 46337
FU3 Unleaded 1542857 89.27 9865
FU4 Unleaded 735294 86.57 12622
FU5 Unleaded 786765 88.73 10403
FL1 LPG 1007353 77.70 22324
BLANK
FINE Blank 0 99.63 0

Dark-stained filters both for fine and coarse filters showed smaller reflectance value.

The measured reflectance value for coarse filters are enumerated in Table 6 and Table 5 for

the fine filters. Filters used for tire pyrolysis have the lowest value of reflectance with

2.80% and 2.93% for the fine (FT1) and coarse filter (CT1) respectively. Filters from the

special fuel, Shell V-power Nitro Plus, exhibited the highest value of reflectance with

89.47% for FS1 and 92.33% for CS1.

Table 6. Coarse load, reflectance and BC concentration

Black
Sample Coarse Load Carbon
Code Source (ng/m3) R% (ng/m3)
CB1 Biomass Burning 23027778 90.53 8600
CB2 Biomass Burning 4227273 87.30 11865
CB3 Biomass Burning 607843 91.30 7842
CT1 Tire Pyrolysis 24833333 2.93 316527
CT2 Tire Pyrolysis 31939024 3.97 289431
CT3 Tire Pyrolysis 13809524 56.53 50879
CP1 Premium 3000000 76.33 23918
CP2 Premium 171429 91.00 8138
CU1 Unleaded 1342466 88.07 11080
CS1 Shell V-power 3114035 92.33 6832
CS2 Shell V-power 1285714 89.53 9597
CS3 Shell V-power 2836957 91.60 7548
CD1 Diesel 3406250 74.93 25580
CD2 Diesel 4590909 76.13 24153
CD3 Diesel 10277778 37.50 87735
CP3 Premium 1057471 89.23 9898
CP4 Premium 1223214 71.57 29707
CU2 Unleaded 1125000 85.67 13561
CU3 Unleaded 421429 91.57 7581
CU4 Unleaded 1632353 91.47 7679
CU5 Unleaded 1661765 90.93 8204
CL1 LPG 661765 88.73 10403
BLANK
COARSE Blank 0 99.63 0

Figure 4 summarizes the result for the calculated black carbon concentration in fine

and coarse filter. The graph shows that the leading contributor of BC are tire pyrolysis

activities. In vehicular sources, emissions from diesel loaded engines showed the highest

BC concentration followed premium gasoline, unleaded gasoline, LPG and the lowest is

the special gasoline (Shell v-power). Filters exposed from biomass burning showed average

amount of BC.
 350000

300000

250000
Black Carbon, ng/m3

200000
Black Carbon in Fine Filters
150000 Black Carbon In Coarse Filters

100000

50000

Source

Figure 4. Black Carbon Concentration of Pollutant Sources

Particles suspended in the coarse filters are identified as PM10 and particles

suspended in the fine filters are identified as PM2.5. The second graph shows that tire

pyrolysis filters CT2 and FT2 has the greatest amount of particulate matter (both for PM10

and PM2.5) followed by biomass burning filters CB1 and FB2. The graph shows

inconsistent trend of the total amount of particulate matter in filters used for biomass

burning. The filters exposed from vehicular emissions showed average amount of total

particulate matter compared to that of the tire pyrolysis.

 60000000

50000000 Total Particulate Mass in Fine Filters

Total particulate Mass, ng/m3

40000000 Total Particulate Mass In Coarse

Filters
30000000

20000000

10000000

Source

Figure 5. PM Concentration of Pollutant Sources

5. Conclusion and Recommendations

Filters exposed from tire pyrolysis exhibited the highest amount of BC and PM. Diesel

engines emissions contribute the highest amount both for BC and PM in terms of vehicular

sources. Special gasoline like Shell V-power Nitro Plus has the lowest amount of PM and

BC out of the other fuel. Unleaded, Premium and LPG fuel showed average amount of BC

and PM concentrations. In Biomass Burning sources, PM and BC concentrations depends

on the material involved. With the result gathered, it is recommended to limit activities

relating from tire pyrolysis. It is also recommended to diesel fuel occasionally.

Moreover, further analyses such as OC/EC and elemental analysis are recommended

to identify specific air pollutants and provide broader information about its chemical

constituents. It is also important to consider several and specific factors such as vehicle
conditions and operating conditions in conducting this kind of study to have a better

interpretation and comparison among these sources. Lastly, it is recommended to prolong

the sampling time to decrease uncertainty.

References

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Analysis and Characterization of Atmospheric Particulate Pollution in
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Wang Xin, Xu baiqing, Ming Jing. An overview of the Studies on Black Carbon and
Mineral Dust Deposition in Snow and Ice Cores in East Asia. Journal of
Meteorological Research. Vol. 28, pp. 354-370, March 8, 2014.
State, Gabriel, Popescu, Ion V., Gheboianu, Anca, Radulescu, Christiana, Dulama,
Iona, Bancuta, Iulian, Stirbescu, Raluca. Identification of Air Pollution
Elements in Lichen Used as Bioindicators, by the XRf and AAS Methods.
National Institute of Physics and Nuclear Engineering, Bucharest-Maguete,
Romania. September 14, 2009.
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Pollution (accessed May 26, 2017.)
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