CHG 201

CHEMICAL
SPECIATION
 TOPIC ONE

INTRODUCTION TO
SPECIATION
1. The key terminologies
Chemical speciation, as summed up by IUPAC,
denotes to distribution of an element among
defined chemical species in a system.
Chemical species: specific form of an element
defined as to isotopic composition, electronic or
oxidation state, and/or complex or molecular
structure.
Speciation analysis: analytical activities of
identifying and/or measuring the quantities of one
or more individual chemical species in a sample.
2.Why chemical speciation
 It is of great interest in scientific community because the
assessment of health hazards, toxicity, bioavailability,
distribution, mobility is based on the levels of specific chemical
form and not on the total element levels/concentration.

 Aimed to help us understand

1. the determination of a particular species in a given sample
involving both identification and quantification

2. species distribution or abundance studies which provide a

description of the numerical distribution or abundance of
different species containing same central element in a given
sample
3.The analytical challenges in chemical
speciation
1. There are difficulties associated with isolating the
compound of interest from complex matrices
2. Most of speciation techniques available do disturb the
equilibrium existing between the various chemical
species in the system of study
3. For the species present at ultra-trace levels, few
analytical procedures posses the degree of sensitivity
required
4. Suitable standard reference material are often
unavailable. Again, different approaches are required for
speciation analysis in water, biological material,
soils/sediments
 4. Experimental approach to speciation
1. Technique selection guidelines
Unique aspects in chemical speciation are
- Procedures adopted should not disturb the existing
equilibrium
- Need for modified/refined technique to handle the
very lower levels present in isolated sub- category
because the element in the sample is near the
detection limit of many standard analytical
techniques.
Cont.
2. Selective measuring techniques
The ideal operation procedure is one that allows positive
identification and quantitative evaluation of the one
particular species
eg. Identification of chemical form of an element which
has toxic properties

3. Preliminary fractionation strategies

Fractionation is a process of classification of an analyte
or a group of analytes from a certain sample according
to the physical or chemical properties
Cont.
Examples:
- Membrane, Filter , Chromatographic methods ,Direct extraction

4. Fractionation of species based on selective sizing

- Sizing based on sieving and centrifuging
Eg. Trace element concentration in soils/sediments
- Utra-filtration and dialysis
Eg. Separation of ionic metal species from colloidal particles
- Gel permeation chromatography
Eg. Separation of species in solution on the basis of molecular
size
 TOPIC TWO

SPECIATION IN
COMPARTMENTS OF THE
ENVIRONMENT
 PART ONE

SPECIATION OF METALS IN THE

ATMOSPHERE
1. Introduction
AIM
- To understand the mechanism of speciation of metals
in the atmosphere.

- To appreciate/show the importance of the speciation of

metals in atmospheric deposition

- To understand the impact of these metals on the marine

environment
Cont.
This is a recent study that comes as the result the
awareness of the ultraclean techniques at all stages of
sample collection and analysis

The study was previously centred on the gaseous non-

metallic compounds (O, C, N, S and halogens)
because of their role in global warming, acid rain,
increase in tropospheric ozone and decrease of
stratospheric ozone.
Atmospheric metals have different mechanism of
interaction between the biosphere and atmosphere and have
also different mechanisms of transport

Metals in the atmosphere are primarily transported on

aerosols which can be removed by wet and dry deposition
processes.

The mechanism by which the biosphere receives the

material from atmosphere is via passive deposition and
direct inhalation

The deposition, the transport and inhalation is controlled

predominantly by the size of the atmospheric aerosols.
Atmospheric cycling of metal
Atmosphere is an important vector of global metal
transport btn regions (ie land to sea and vice versa).

The atmospheric deposition of acid on the terrestrial

system affects the mobility of metals during
weathering process.
(Pelletier, 2021)
 Atmospheric aerosol

An aerosol is a suspension of fine solid particles or

liquid droplets in air or another gas with a diameter
between 0.002 to 100 nanometers.
Aerosol particles vary greatly in size, source, chemical
composition, amount and distribution in space and time,
and how long they survive in the atmosphere

Aerosols can be natural or anthropogenic

 Atmospheric aerosol classification
1) particle size:
 fine mode (d < 2.5 μm) which is divided into
- the (Aitken) nuclei mode (about 0.005 μm < d < 0.1 μm)
- the accumulation mode (0.1μm < d < 2.5 μm).
 coarse mode (d > 2.5 μm);
2) chemical composition: sulphate, nitrate, soot (elemental
carbon), sea-salt (NaCl); etc.
3) geographical location: marine, continental, rural,
industrial, polar, desert aerosols, etc.
4) location in the atmosphere: stratospheric and
tropospheric aerosols.
Aerosol chemical speciation
The main technique employed for this is called
Sequential Extraction (ie 3 Stage Sequential
Extraction)
1. Stage one: a weak leaching agent is used to release
the exchangeable metals (water and acid soluble)
through adsorption and condensation
2. Stage two: a strong leaching agent is used to release
reducible metals held on iron and manganese oxides
3. Stage three: a very strong leaching agent is used to
release the oxidisable metals bound to organic
substances and sulphides.
Techniques used in the analysis of single aerosol particle

Scanning Electron Elemental analysis of asingle particle

Microscopy
Energy Dispersive X-ray
Spectroscopy
X-ray diffraction Characterisation of crystalline phases

Particle induced X-ray Detection of elemental composition of

Emission Spectrometry single particles
Extractive Electrospray Ionisation and analysis of the aerosol
Ionization Mass phase
Spectrometry
Atmospheric aerosol removal
Atmospheric deposition is an important process that
removes gases and particles from the atmosphere.
1. Dry deposition
This is a free fall of the atmospheric trace gases and
particulate matter to earth directly from the
atmosphere
Eg. This is for crustally derived particles eg. Fe and Al
2. Wet deposition
A process whereby atmospheric gases mix with
suspended water in the atmosphere and are washed
out through rain, snow or fog.
This for very small particles eg. Lead, zinc, nickel
Depositional processes are affected by

1. Spatial fluctuation
2. Surface-type differences
3. Temporal changes
4. Diurnal variations
5. Meteorological conditions
Trace metal solubility
The subsequent fate of trace metals depends on
their solubility.
The solubility depends on the element and the
particle size
Metals contained in the carbonaceous aerosols
(adsorbed impurities and salts) are easier dissolved
than from the alumino-silicated particles.
The former is hardly dependent of pH, the latter is
highly influenced by pH
Chemical speciation of metal in rain water
and aerosols
Oxidation state of metals plays a greater importance
within the atmospheric samples
The oxidation state governs the
1. Chemistry of the metal in the atmosphere together
2. Biological availability of the element
3. Toxicity of the element
Some aerosols show physico-chemical differences
between the oxidation states
Manganese
1. Mn(IV) is insoluble in water and Mn (II) is water soluble
It is released into the atmosphere as PM
In water it exists as both Mn(IV) and Mn(II) but Mn(II) dominates at
low pH

 Arsenic
1. As(III) can be oxidized to As(V). All these are coal and smelting
sources
In atmosphere it is released as arsenic trioxide and exists are
particulate matter
In water it exists as Arsenate (pentavalent) and Arsenate (trivalent),
but the former predominates under oxidizing conditions and the
latter under reducing conditions
The dominant anions in the rainwater are chloride,
sulphite, sulphate, hydroxide.
Dissolved metals in wetted aerosols and rainwater
occur as the aquated free ions or in complexes of the
above anions
For example: Mn(II) and Ni(II) occur as hexaqua ions
The role of organic complexation
Organic material is a major and variable
component of aerosols and rainwater

The organic compounds tend to undergo a variety

of reactions including oxidation and reduction or
addition of some ligands or ions.

These reactions yield series of complex

intermediaries having metal complexes
 Examples of candidate organic ligands in the atmosphere are
1. Monofunctional compounds eg. Alcohol, aldehydes
These complex only weakly with transition metal ions

2. Dicarboxyl acids eg oxalic acid

These are prime candidates for the atmospheric ligands and lead to
substantial trace metal complexation

3. Hydroxy acids
These sow great potential to form complexes

4. Macromolecular ligands eg humic and fulvic acid

These are able to bind very strongly with metal ions are abundant within
Mercury in atmosphere
 Mercury is one of the contaminants of most concern because of
its high toxicity, persistence and accumulative behaviour in the
environment and biota

 Atmospheric mercury can be categorized into

1. Total Gaseous Mercury (TGM) a.k.a Vapour Phase Mercury
- Gaseous Elemental Mercury (GEM, Hg°)
- Reactive Gaseous Mercury (RGM, Hg2+) a.k.a Gaseous
Oxidised Mercury (GOM)

2. Particulate-bound Mercury (PBM, Hg P) a.k.a aerosol phase

mercury
 GEM
This contributes over 95% of TGM
It has very low solubility in water
Its chemical reaction rate with other components in the
atmosphere (ozone ) is very low.
However, during long distance transport, it can react
chemically with the atmospheric oxidants resulting in
the formation of Hg(II) which is water soluble
It has long atmospheric life (residence) time and can be
transported across thousands of kms through
atmosphere.
RGM/GOM
It can be emitted from anthropogenic point sources
It is primarily formed by atmospheric oxidation
reaction of GEM with ozone, hydroxyl radical,
nitrate, peroxide or halogens.
It occurs in association with variety of organic and
inorganic ligands such as halides and hydroxyl ion
The compounds can be scavenged on to the
aerosol phase (PBM) and be deposited by wet and
dry deposition
It has shorter atmospheric residence time.
 PBM
This consists of all airborne particulate containing
Hg, including stable condensed and gaseous forms
adsorbed on the atmospheric particulate matter
It includes all those particles with diameter less than
2.5micrometer
This is a converted GOM upon adsorption/absorption
on aerosol particles
It usually accounts for less that 10% of the total
atmospheric mercury
It is much more efficiently scavenged by rain-water
The organic mercury

Methyl mercury is the dominant species in the

biological environment
It is produced by micro-organisms (ie.bacterial
methylation) and is emitted as mono-methylated or
di-methylated mercury to the atmosphere.
The volatile methylated forms are most toxic
forms of mercury and they constitute significant
environmental hazard
Biogeochemical effects of atmospheric
inputs on the ocean.
The atmospheric input of chemicals to the ocean is
closely related to a number of important global
change issues
There is a growing recognition of the impact of the
atmospheric inputs of both natural and
anthropogenic substance on ocean chemistry,
biology and biogeochemistry
Of importance is the oceanic iron as it is a limiting
nutrient towards biological productivity in many
areas of the ocean
The availability of this oceanic iron depends on it
chemical speciation which in turn is predominantly
affected by its solubility

It is significantly reduced to Fe(II) at low pH due

to atmospheric oxidation of Fe(III) or
photochemical reduction of [FeOH(H2O)5]2+
through photoreactive Fe(III)-oxalate complexes
The effects of oceanic iron

- It influences algal community structure and productivity

- It may limit Nitrogen fixation by photosynthetic
diazotrophs (creates low nitrate concentration in surface
water)
- It results in the species shifts and changes in the
phytoplankton size distribution
- It changes oceanic CO2 uptake by altering the efficiency
of organic carbon export