Atmospheric Analysis

Particulates

What is particulate matter?

The term particulate matter (PM)
includes both solid particles and liquid
droplets found in air.

What is particulate matter?

Particulates are a natural component of the atmosphere.
They include the following:

Condensation products from natural combustion (forest

fires, volcanoes, etc.).
Products of reaction of trace gases (ammonium
chloride, sulfate and nitrate salts).
Material dispersed from the earths surface (salt spray
from oceans and mineral dust from continental land
mass).
In addition to these is the particulate material
introduced by man. This can predominate in urban
atmospheres, with the major sources being combustion
and incineration processes.

Which measurements may be useful

for characterization of the particulate
content of an atmospheric sample:
(i) A preliminary measurement would be the total
particulate
concentration.
This
is
a
measurement of the weight of solid extracted
from a fixed volume of the atmosphere by
filtration or by other methods
Typical values are as follows:
70 g m3 rural air
300 g m3 urban air
10 mg m3 factory workshop air
100 mg m3 power station flue gases

Which measurements may be useful

for characterization of the particulate
content of an atmospheric sample:
The second consideration is the analytical
composition.
For metals, this is often simply elemental analysis.
The analytical task can be more difficult than we
found for aquatic samples since the inorganic
component of the particulate material may be
highly insoluble, particularly if present as silicate
salts. All of the analytical techniques we have so
far come across involve sample dissolution.
(ii)

(iii)

The particle size distribution is often also

determined.

Why do you think particle size is important?

1. Transport.
The residence time of a particle in the
atmosphere is dependent on its size.
The greater the size, then the more
rapidly deposition from the atmosphere
occurs

Transport.

Why do you think particle size is important?

2. Differences in Physiological Properties.
The smaller the particle size, then the greater is
the possibility of the particle entering the gas
exchange region of the lungs.
It is this material which will have the greatest
potential physiological effect. This fraction of
the particulate matter is termed respirable
dust, and as a guide would refer to material
below approximately 5 m.

Why do you think particle size is important?

3. Distribution of Chemical Species.
If you are studying emissions from a particular
industrial process, you may find that the
particulate matter is often within a narrow size
range.
Fractionation of the dust sample may then constitute
an essential part of the analytical procedure.
Particle size measurements will be important in
determining the most suitable method of pollution
control.

Why do you think particle size is important?

4. Effect on Atmospheric Reactions.
We have seen that many reactions take
place on the surface of particles.
The surface area per unit mass decreases
with an increase in particle size for
similarly shaped particles.

PM10
Particles up to 10 micrometer in diameter.
These can occur from a number of sources.
Road transport can contribute up to 50% in
an everyday city atmosphere
Other sources include power stations and
coal fires.

PM2.5
Particles up to 2.5 micrometer in diameter is
referred to as fine particles (In comparison,
a human hair is about 70 microns in diameter.)
Fine particles result from many different sources
including
industrial
and
residential
combustion and vehicle exhaust so their
composition varies widely.
Fine particles can also be formed when
combustion gases are chemically transformed
into particles.

AQI: Particulate Matter (PM)

Index
Values

Levels
of Health
Concern

0 - 50
51 - 100**

101 - 150

Cautionary Statements*
PM2.5

PM10

Good
Moderate

None
None

None
None

Unhealthy for
Sensitive
Groups

People with
respiratory or
heart disease,
the elderly, and
children should
limit prolonged
exertion.

People with
respiratory
disease, such as
asthma, should
limit outdoor
exertion.

AQI: Particulate Matter (PM)

Index
Values

151 - 200

201 - 300

Levels
of Health
Concern

Unhealthy

Very Unhealthy

Cautionary Statements*
PM2.5

PM10

People with
People with
respiratory disease,
respiratory or heart
such as asthma,
disease, the
should avoid outdoor
elderly, and
exertion; everyone
children should
else, especially the
avoid prolonged
elderly and children,
exertion; everyone
should limit
else should limit
prolonged outdoor
prolonged exertion.
exertion.
People with
respiratory or heart
disease, the
elderly, and
children should
avoid any outdoor

People with
respiratory disease,
such as asthma,
should avoid any
outdoor activity;
everyone else,

Sampling Methods
High-Volume Air Samplers (HVAS)
In this method, the air sample is drawn
through a large-diameter membrane
filter (2025 cm), typically at 75 m3 h1.
Typical sampling times range from 1 h for
contaminated urban atmospheres to 12 h
for clean rural atmospheres.

Schematic of a HVAS

PM-10 Sampler
Add-on to standard
Hi-Vol sampler
Remove large particles
via impaction or settling
chambers

 Choice of filter depends on analyis

Glass fiber finely spun borosilicate
fibers with binder
Cellulose
Membrane - microporous plastic films
made from a variety of polymers

Filters

Filters

Chose correct filter for

analyses
Retain correct size
Absence of impurities
Compatible with
analytical procedure

Source: Wight, 1994

Filters
Pros

Cons

Glass FIber

- Low water uptake

- High efficiency for particles > 0.3 m
- Resistant to high T

Cellulose

- Low head loss

- Low metallic contamination level
- Easily ashed

- Hydrophillic

Membrane

- Flat for microscopic analysis

- Hydrophobic
- Chemically resistant

- Large head loss

- Brittle
- Not resistant high T

Use

Organics

Metals +
inorganic ions

Question
Calculate the PM-10 concentration for the following conditions:
Filter mass gain = 0.000670 mg
Sample time = 1446 min
Initial sampler flow rate = 1.875 cm3 min-1
Final sampler flow rate = 1.807 cm3 min-1

Average flow rate = 1.841 cm/min

Volume of air = 1.841 cm3/min x 1446 min = 2662 cm3 = 2.662 x10-3 m3
PM concentration = 6.70 x 10-1 g / 2.662 x 10-3 m3 = 251.7 g m-3

Polyurethane Foam Sampler (PUF)

For organics need both solid and vapor phases

Vapor cartridge is placed in-line with quartz fiber
filter for semi-volatile organics
PUF plug
Adsorbent resin (XAD-2)
If vp is high VOCs may
be in aerosol form
- Pesticides
- PCBs
- Dioxins
- PAHs

Cascade Impactors

Uses adhesion of PM rather

than filtration
Flow is constricted, velocity
increases
Successively smaller particles
adhere to each successive
surface
Fractionated according to mass
2.5 10 m / < 2.5 m

Flow Calibration

Source: Wight, 1994

B. Beta Attenuator Methods (BAM)

Beta particles from 14C source are

attenuated (lose signal strength) as
they pass through particulate deposits
on a filter tape
Absorption of radiation is proportional
to mass of PM
Contunuous real-time
measurement
(no weighing required!)
Range: 30 - 300 g/m3
Temperature: -30 to +45C
New version is heated to remove
moisture effects

http://www.thermo.com/

C. Tapered Element Oscillating

Microbalance (TEOM) Methods

Air is drawn through a filter at the end

of a a tapered oscillating glass tube
Change in frequency is directly
related to the mass of PM
accumulated
Range: 30 - 300 g/m3
Temperature: -30 to +45C

Reeve, 2002

D. Nephelmeter

Optical method
Similar to turbidimeter

Scattering of light by
suspended PM, detection by
photomultiplier tube. Baffles
minimize reflected light

Question
There are currently several investigations to compare the results of
different PM analyzers. What reasons could contribute to this
concern?

Measurements are dependent on atmospheric conditions

Absorbed water may be difficult to control during operations
Meteorological conditions may affect flow rate
Each technique responds differently to individual particle sizes
Some components are volatile and may be lost due to heat
(TEOM)

MASA: 501
Principle: air is drawn through a 8 x 10 filter at a known
flow rate
Mass of particles is determined by the difference in filter mass
prior to and after sampling
Concentration of suspended particulate matter is calculated by
diving the mass gain of the filter by the volume of air sampled

Lodge, 1988

PERHITUNGAN TOTAL SUSPENDED PARTICULATE

(W1 W0 ) x10 6
TSP
V std

dalam g / std m3

Dimana ;
W1 = berat akhir kertas saring setelah digunakan, g
W0 = berat awal kertas saring sebelum digunakan, g
106 = konversi gram ke g
Vstd = volume sampel udara yang dikoreksi berdasarkan standar tekanan EPA
(760 mm Hg) dan standar temperatur (250C), m3

The choice of filter is based on the

following:
Retention of correct particle size range.
Absence of trace impurities in the filter.
Compatibility with the subsequent analytical
procedure. Some procedures require the total
combustion of the filter, and others its
dissolution.
Cellulose filters should be used for metals and
inorganic anions, and glass-fiber filters (or
under some circumstances, silica filters) for
organics.

Analytical Methods Involving

Sample Dissolution
Metals
A first step in any analytical procedure should
be to consider the probable composition of the
sample.
This is a vital step for particulate analysis which
will allow the correct choice of dissolution
technique.
If the composition of the sample is unknown, as
would be the case for many external
atmosphere samples, hydrofluoric acid, which is
capable of dissolving silicates, may be required.

Analytical Methods Involving

Sample Dissolution
Metals
This acid causes severe burns and attacks
glass apparatus (the silica structure of the
glass is closely related to the insoluble
silicates which you may be trying to
dissolve).
Teflon apparatus is required and the
analyses should be performed in a hydrogen
fluoride-resistant fume cupboard.

Analytical Methods Involving

Sample Dissolution
Metals
If the composition of the dust sample is known
(as may be the case with samples from
workplace environments), the dissolution may
be less severe, according to the known
solubility of the sample.
Dilute acid, mild oxidizing agents, or even
water may be all that is necessary for
dissolution.

Analytical Methods Involving

Sample Dissolution
Logam Pb
Destruksi kering
Sampel filter total partikel tersuspensi di udara ambien
yang dikumpulkan dalam filter HVAS dikeringkan
dalam oven pada suhu 100 oC selama 2 jam, lalu
masing-masing sampel kering diambil dan ditimbang
beratnya kemudian dimasukkan ke dalam gelas
beker dan ditambahkan 10 ml larutan Mg(NO 3)2 10 %.
Campuran diaduk, kemudian gelas beker dipanaskan
untuk menguapkan alkohol. Sampel dipindahkan
dalam krus porselin dan dikeringkan dalam oven
selama 10 jam pada suhu 450 oC.
Kemas M. Fahriza, 2006

Analytical Methods Involving

Sample Dissolution
Logam Pb
Destruksi kering
Sampel dikeluarkan dan didinginkan, setelah dingin
ditambahkan HNO3 sampai abu terbasahi.
Sampel dimasukkan kembali dalam oven dan
dipanaskan pada suhu 450oC selama 2 jam. Sampel
dikeluarkan dan didinginkan, setelah dingin
ditambahkan 10 ml larutan campuran asam untuk
melarutkan sampel. Larutan diencerkan dengan
akuabides sampai volumenya 100 ml.
Kemas M. Fahriza, 2006

Analytical Methods Involving

Sample Dissolution
Logam Pb
Destruksi basah

Sampel total partikel tersuspensi di udara ambien

yang dikumpulkan dalam filter HVAS dikeringkan
dalam oven pada suhu 100 oC selama 2 jam, lalu
masing-masing sampel kering diambil dan
ditimbang beratnya kemudian dimasukkan ke
dalam gelas beker dan ditambahkan 25 ml HNO 3
pekat, lalu ditutup dengan gelas arloji.
Sampel disaring dan residunya dicuci lagi dengan
HNO3.
Kemas M. Fahriza, 2006

Analytical Methods Involving

Sample Dissolution
Logam Pb
Destruksi basah
Filtrat hasil penyaringan kemudian diuapkan
sampai hampir kering.
Larutan didinginkan, kemudian perlahan-lahan
ditambahkan 8 ml HClO4 pekat 60 %.
Larutan dididihkan sampai hampir tidak berwarna.
Sampel didinginkan, kemudian ditambahkan 1 ml
HCl pekat, larutan disaring dan selanjutnya
diencerkan sampai volumenya 100 ml.

Kemas M. Fahriza, 2006

Which two methods have you come across which

may be most suitable for routine analysis of
metals in particulates?
Answer
(i) Atomic absorption spectrometry
(ii) Ultraviolet/visible absorption spectrometry
For less routine analysis, and particularly for analysis of
metals at low concentrations, other techniques may
sometimes be used.
These include inductively coupled plasma-optical
emission,
inductively
coupled
plasma-mass
spectrometry, flame atomic emission and atomic
fluorescence techniques. Ion chromatography can also
be used for common main group metal ions (Na+, K+,
Ca2+ and Mg2+)as well as for common anions.