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Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Scavenging
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Definition:
Scavenging is a process of sticking onto particles.
A chemical agent that is added to a chemical mixture to
counteract the effects of impurities.
Scavenging is a process of sticking onto particles and this
heavier particles fall to the bottom of the ocean.
In the Gulf of Alaska, Phosphorous is abundant so the
other trace metal such as Fe could be the limiting factor.
So if the rate of scavenging increases that would
decrease the Fe in the water column which could
decrease the biological productivity.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

A scavenger in chemistry is a chemical substance added to a mixture in order to


remove or inactivate impurities or unwanted reaction products.
Their use is wide-ranged:
1. In atmospheric chemistry, the most common scavenger is the hydroxyl radical, a
short-lived radical produced photolytically in the atmosphere. It is the most
important oxidant for carbon monoxide, methane and other hydrocarbons, sulfur
dioxide, hydrogen sulfide, and most of other contaminants, removing them from
the atmosphere.
2. In molecular laser isotope separation, methane is used as a scavenger gas for
fluorine atoms.
3. Hydrazine and ascorbic acid are used as oxygen scavenger corrosion inhibitors.
4. Tocopherol and naringenin are bioactive free radical scavengers that act as
antioxidants; synthetic catalytic scavengers are their synthetic counterparts
Synthetic Catalytic Scavenger is an artificial anti-oxidant that has been
demonstrated to extend cellular life.
5. Organotin compounds are used in polymer manufacture as hydrochloric acid
scavengers.
6. Oxygen scavengers are small sachets or self adhesive labels that are placed
inside modified atmosphere packs to help extend product life (notably cooked
meats) and help improve product appearance. They work by absorbing any
oxygen left in the pack by oxidation of the iron powder contained in the
sachet/label.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Scavenging in Atmosphere
In wet deposition, there are always some atmospheric hydrometeors which
scavenge aerosol particles. This means that dry deposition is
gravitational coagulation with water droplets.
Different types of wet deposition include:
1. Precipitation scavenging. This is where falling rain droplets collide with
particles. This is also called "below-cloud scavenging".
2. In-cloud scavenging. This is where aerosol particles collide with the
water droplets in clouds. A common example of this type of deposition is
inside fog. Clouds may also intercept with terrain (e.g. onto a mountain).
3. Snow scavenging. This is where falling snow "removes" the material
below it.
At the point of stack emission and during atmospheric transport, mercury
can also become bound to particulate matter. This form of mercury,
Hg(p), can be removed from the atmosphere by both wet deposition
(precipitation scavenging)
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

scavenging coefficient
International Society of Coating Science and Technology (ISCST) models
wet deposition using rainfall intensity and an empirical parameter known
as the scavenging coefficient.
The total flux to be deposited is the product of the scavenging ratio
multiplied by the concentration integrated over the vertical dimension.
The scavenging ratio is composed of two parameters, precipitation
intensity (mm/hr) and a scavenging coefficient (s-mm/hr)-1.
The scavenging coefficient depends on the characteristics of the pollutant
(e.g., solubility and reactivity for gases, size distribution for particles) as
well as the nature of the precipitation (e.g., liquid or frozen).
Scavenging rate coefficients are expected to be approximately 1/3 smaller
for frozen precipitation.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Direct measurements of scavenging parameters for mercury are not available.


However, estimates of a washout ratio, (concentration in precipitation to
concentration in air), were provided in the EPAs report (1998c). The washout
ratio can be related to the scavenging coefficient used in ISCST. The washout
ratio for reactive gaseous mercury is 1.6 X 10-6, while the ratio for elemental
mercury is 1200. The large difference reflects the much higher solubility of
reactive gaseous mercury. Using these values, the scavenging coefficient was
calculated as 2.5 X 10-4 (s-mm/hr)-1 for reactive gaseous mercury and 3.3 X 107 (s-mm/hr) -1 for elemental mercury.
Table: Wet Deposition Parameters of Mercury.

Form of Mercury Liquid Scavenging


Coefficient (s-mm/hr)-1

Frozen Scavenging Coefficient


(s-mm/hr)-1

Hg(0)

3.3 X 10-7

1.0 X 10-7

Hg(+2)

2.5 X 10-4

5.0 X 10-5

Hg(p) 0.68 m

7.0 X 10-5

2.0 X 10-5

Hg(p) 3.5 m

2.8 X 10-4

9.0 X 10-5

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Scavenging in Water
Generally, trace elements are being scavenged during the course
of transportation, particularly in the ground water and ocean.
When the ground water is squeezed out, during its upward
movement it corrodes the minerals primarily like scavenging.
Such affixation, or bonding, takes place always from week to very
strong.
The strength of the bonding on the host depends on the chemical
nature, weak electrostatic attraction, etc.
Such scavenging is carried over mostly by hydrated aluminium
silicates (clays), secondary carbonates, amorphous oxides of
manganese and oxides of iron.
While leaching such scavenged trace elements, one should apply in
the host mineral, the order of increasing bond strength such as clays
first and then crystalline iron oxides last.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Such scavenging property enable the migration of


elements along with the associated media from other
sources from those normally presently in the over burden.
In Naveda, gold deposits are being deducted by the
occurrence of gold or its associated elements arsenic and
antimony.
Elemental scavenging by geochemical particles in
estuaries and coastal waters plays an important role in
determining the behaviour and incident concentrations of
trace metals and other pollutants.
Further offshore biological processes become increasingly
important in regulating the flux of these materials,
dominating this process in oligotrophic regions.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

The generation of re-suspended particles at the ocean boundaries also


can have an important electron the distributions of dissolved elements in
sea water.
This arises because the higher concentrations of fine particles at the
boundaries lead to zones of enhanced particles at the boundaries lead to
zones of enhanced scavenging.
Thus, processes at the ocean boundaries may act as a source for fine
particles and as a sink for some dissolved elements via enhanced
scavenging.
Although, the vertical transport of elements down the water column by
incorporation into the sinking particle thus, and reference to scavengingtype and nutrient-type processes, offers a useful insight into it is how
trace elements are removed from sea water it is evident that lateral
transport into and out of the boundary regions (e.g., along isopyenas)
must also be considered in assessing the processes that control the
marine cycles of the trace elements.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

The scavenging removal itself is dominated by the fine-particle


population, but is then complicated by as association of the fine
particles with the large-particle thus by reverable physical
mechanisms and by reversible chemical adsorption that may tend
towards an equilibrium state.
A number of carrier phases, and types of association, are possible
between trace elements and marine particulates.
According to Collier & Edmond (1983) these trace element association
include:

(i) those with terrigenous material scavenged by biogenic particles,


(ii) those involving
metabolism;

specific

biochemical

processes

related

to

(iii) those with structural skeletal materials such as cakite, opal and
celeatite, and
(iv) those with hydrous metal oxide precipitates, or organics, via active
surface scavenging.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Factors:
Inorganic:

The surface chemistry.


The basis of equilibrium constants
Bond strength or susceptibility.

Organic:
The trace-metal scavenging is controlled by organic
coatings

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Biogenic Particle Cycle

Photosynthesis (in euphotic zone) and


formation of biominerals.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Particle cycle

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Two major processes of particle


formation

Uptake of elements (nutrients) and


subsequent transport and remineralization

scavenging: adsorption
desorption from) particles

onto

(and

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Solute adsorption
the surface ligand model
Surfaces of aquatic particles contain acidbase functional groups other coordination
properties
Surface adsorption reactions consist both
of a chemical bonding of solutes to
surface atoms and an electrostatic
interaction between ions and charged
surfaces
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

What makes surfaces different?


Weak acid groups - The tendency of groups to
coordinate a proton will decreases as the overall
surface charge increases in positive charge. Net
result of increasing positive charge = decreasing
protonation constant
Steric effects - The geometry of solid surfaces
can affect the degree of dehydration for
coordinated species with respect to their
geometric analogs in solution. Thus, similar sites
can display substantial variation in their
coordination properties
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Adsorption of metals & ligands on


particles
e.g. oxide surfaces
Use of OH- as a model ligand
XOH is a general hydrolyzed metal species (Si,
Al, Fe, and Mn)

acid/base reaction
XOH = H+ + XO-

XOH + H+ =
XOH2+
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Possible coordination species

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Carbonate and sulfide ligands


Some surfaces are not dominated by hydroxyl groups,
but by other groups, such as carbonates or sulfides
ex. calcite (CaCO3)
Ca+ + H2O = CaOH + H+
CO3- + H+ = HCO3
ex. cadmium sulfide (CdS)
Cd+ + H2O = CdOH + H+
S- + H+ = SH

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Oxidative scavenging - Fe and Mn


Short lifetime of reduced elements such as
Fe(II) (~mins to hours) and Mn(II) (~70
yrs); both insoluble in oxidized state
Fe has a nutrient profile
Mn has a scavenged profile
Both can be affected by oxygen minimum
zones
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Oxidative scavenging - Fe and Mn


Fe(II) and Mn(II) can form insoluble oxides ferromanganese nodules

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

FOUND IN NODULES
Mn(II) / Mn(IV)
Fe(II) / Fe(III)

Co(II) / co(Ill)
Pt(II) I Pt(IV) ?
TI(I) /TI(III)
Pb(II) / Pb(IV)
Ce(III) / Ce(IV)

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Hydrolytic scavenging
Al, Bi, Cr(III), 232Th, Sn, Te
No obvious oxidative removal pathway
Deep sea concentration profiles are
dominated by scavenging - invariably fairly
strongly hydrolyzed

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Estimating scavenging using U- Th

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Coale and Bruland 1987

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Oxidative reaction
An antioxidant is a molecule capable of slowing or preventing the
oxidation of other molecules.
Oxidation is a chemical reaction that transfers electrons from a substance
to an oxidizing agent.
Oxidation reactions can produce free radicals, which start chain reactions
that damage cells.
Antioxidants terminate these chain reactions by removing free radical
intermediates, and inhibit other oxidation reactions by being oxidized
themselves.
As a result, antioxidants are often reducing agents such as thiols or
polyphenols.

Some compounds when dissolved give off H. Some give OH or other


molecules which scavenge H. Compounds that increase H are acids;
those that decrease H are bases.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Oxidative reaction
A variety of oxygen transport and binding proteins exist in organisms
throughout the animal and plant kingdoms.
Organisms including bacteria, protozoans and fungi all have hemoglobinlike proteins whose known and predicted roles include the reversible
binding of gaseous ligands.
In particular, the distinction of myoglobin and hemoglobin in lower
animals is often impossible, because some of these organisms do not
contain muscles.
Or, they may have a recognizable separate circulatory system but not one
which deals with oxygen transport (for example, many insects and other
arthropods).
In all these groups, heme/globin containing molecules which deal with gasbinding are referred to as hemoglobins. In addition to transport and
sensing of oxygen, they may also deal with NO, CO2, sulfide compounds,
and even O2 scavenging in environments which must be anaerobic.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Bacterial protection:
A proper iron metabolism protects against bacterial infection. If bacteria
are to survive, then they must get iron from the environment.
Disease-causing bacteria do this in many ways, including releasing ironbinding molecules called siderophores and then reabsorbing them to
recover iron, or scavenging iron from hemoglobin and transferrin.
The iron-deprived bacteria reproduce more slowly.
So our control of iron levels appears to be an important defense against
bacterial infection.
People with increased amounts of iron, like people with hemochromatosis,
are more susceptible to bacterial infection.
Iron is also stored as a pigment called hemosiderin in an apparently
pathologic process.
This molecule appears to be mainly the result of cell damage. It is often
found engulfed by macrophages that are scavenging regions of damage.
It can also be found among people with iron overload due to frequent
blood cell destruction and transfusions.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Scavenge (free radicals):


Free radicals are highly reactive compounds generated through various
chemical reactions which cause damage to cells.
Most free radicals are oxygen derived byproducts of normal cell functions
like aerobic respiration (like Hydrogen peroxide, and superoxide anion).
Free radicals are chemical species that have a single unpaired electron in
the outer shell.
Ex: OH- free radical attacks lipids, it converts the lipid into a lipid peroxide
which is in itself a free radical that can go on to damage other lipids.
Lipids make up the cell's membrane which functions to control the cell's
internal versus external chemical environment.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Scavenge (free radicals):


Macrophages are stimulated to take up oxidized compounds via their
"scavenger receptors", and this is especially seen when taking up oxidized
cholesterol.
Free radical scavenging compunds like Vit E, and Vit C work by reducing
the action of free radicals and thus preventing cell damage in the first
place.
Once the process has started though, Vit E and C scavanging has little to
do with inflammation prevention.
So in the end, free radical scavengers are good for preventative therapy,
though there is still much debate upon how much good they really do.

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Unit : I

Title : Scavenging

Free radicals:
Some internally generated sources of free radicals are:
mitochondria
phagocytes
xanthine oxidase
reactions involving iron and other transition metals
arachidonate pathways
peroxisomes
exercise
inflammation
ischaemia/reperfusion.
Some externally generated sources of free radicals are:
cigarette smoke
environmental pollutants
radiation
ultraviolet light
certain drugs, pesticides, anaesthetics and industrial solvents
ozone.
Lecturer N.Muthukrishnan, CARISM, SASTRA University

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