POSSIBLE CAUSES AND HAZARDS OF NOX GASES EVOLVED

AFTER SURFACE BLASTING.

By: Dr. Atul P Dwivedi

With the increasing restrictions from the government regarding the Emissions from the open
cast coal and other mines, the Indian coal and other mines are coming under greater
constraints regarding their environmental impacts i.e. Hazards. The problems of NOx have
been increasing in the recent past because of the rapid expansions of the open cast coal and
other mines and also due to the large number of new mines. The frequency and the volume of
the NOx generated have been increased many times and because of this the hazards
associated with the emission of fumes have also increased. This paper reviews the possible
causes and hazards associated with the Emission of NOx after surface blasting.

1. INTRODUCTION:
Due to rapid industrialization and also because of the increase in number of coal based power
plants the mining activities had been increased many times. Due to this the large quantity of
explosives are used. In India the open cast coal and other mines are widespread, in central
India with several large mines operating in the close proximity to the cities and villages, there
is a huge concern regarding the possible environmental impact of the mining on the nearby
population and also to the workers associated with the mining operations.

As it is widely known, blasting operations are extensively used in all sectors of the economy.
The blasting energy is the cheapest which people use in their activity. Historically blasting
operations have been extensively used for excavation of inert materials and mineral
exploration. Now days we could hardly imagine production process in any surface mining
operations at ore mines and quarries and in the construction industry, not involving blasting.
This extensive use of explosives and blasting operations, however, inevitably poses some
environmental issues as the not completely controlled negative effects of blasting, the seismic
effects, extensive fuming among many others.

The blasting action of the Explosive is because of production of large quantities of expanding
gases produced as it detonates. Ideally, the gaseous detonation products of explosives would
consist of water (H2O), carbon dioxide (CO2), and nitrogen (N2). Due to the kinetics of the
chemical reaction, the detonation of explosives in a blasting operation also produces toxic
nitrogen dioxide (NO2), nitric oxide (NO), and carbon monoxide (CO). This may be because of
many reasons which will be discussed later in this paper.
2. CAUSES AND HAZARDS OF NOX GASSES:
There are many causes of emission of NOx after surface blasting and the related hazards have
been discussed in this paper.
2.1 Causes of NOx emissions:
It is well know that the explosives which are used in open cast mines are generally
ammonium nitrate/ANFO based.
2.1.1 The general chemical reaction that takes place during blasting is as follows:
CnH2n+2 + (3n+1) NH4NO3 nCO2 + (7n+1) H2O + 3nN2 ................... (1)

In Ideal condition the gaseous products produced from the explosion are carbon dioxide
(CO2), water vapour (H2O) and nitrogen (N2).
The balanced equation for an ideal explosive reaction is as follows:

3NH4NO3 + CH2 3N2 + 7H2O + CO2 ........................... (2)

This is an oxygen balanced explosive reaction that does not generate NOx.
During mining operations it is not possible to maintain the ideal condition of blasting and due
to which the following reactions takes place.
A non ideal explosive reaction is as follows:
5NH4NO3 + CH2 4N2 + 2NO + CO2 + 11H2O ..................... (3)

2NH4NO3 + CH2 2N2 + CO + 5H2O ........................ (4)

The above reactions because of the small changes in the stoichiometry of reaction substantial
amount of toxic gases such as carbon monoxide and nitric oxide are produced, which are
harmful for the environment and the human health.

The nitric oxide combines with oxygen in the atmosphere to produce nitrogen oxide.
2NO + O2 2NO2 ........................... (5)

During the blasting huge quantities of NO2 is produced and this can be observed by the
yellowish orange or reddish brown plumes which rises above the blasting site in large
quantity as shown in the figure 2.1.
Every Kilogram of diverted along reaction path (3) and then to (5) generates over 110 litres
of NOx.

Fig 2.1 The figure of open cast mines.

2.1.2 The Experimental results:-

In the laboratory the trail were made using pure ammonium nitrate, ammonium nitrate based
explosives and using the ANFO blends in different proportions the results were:
2.1.2.1 In the first case were only the ammonium nitrate had be blasted alone the large
amount of reddish yellow colour fumes had been generated giving the indication about the
large amount of NOx had been emitted.
2.1.2.2 In the second case when the amount of fuel in limited to the extent to which it is
required in the formulation the blast will not produce the NOx as indicated by the colourless
fumes generated after blasting.
2.1.2.3 In the third case the fuel was more than the required quantity the NOx emission was
visible as indicated by the reddish orange fumes.
2.1.2.4 In the last case the fuel was less than the required quantity due to this the purple/
brown fumes were generated indicating the presence of the NOx.

2.1.3 The reason for the generation of NOx fumes:

The main reasons for the generation of the NOx fumes are the unbalanced formulations i.e.
the oxygen balance of the reaction was not properly calculated, if the reactions oxygen
balance is zero then the reactions products will be water vapour, carbon dioxide and nitrogen
with colourless plumes, if the reactions oxygen balance is negative this will create deficiency
of oxygen cause emission of toxic gasses and if the oxygen balance is positive this will create
excess of oxygen and thus causes the emission of toxic gasses with nice red colour plumes.
This problem can be solved by suitably designing the formulation such that its oxygen
balance should be zero or nearer to zero.

The fumes are also generated because of the Chemical formulation of the mixed explosives
and/or precursors unknowingly or inherently designed to generate fume, Formulation of
explosives mixture and/or precursors having small ranges of optimal sensitivity, Formulation
of explosives mixture and/or precursor having limited conditions of stability, Formulation of
explosives mixture and/or precursor insufficiently resistant to conditions it is used in.
Formulations of explosives mixture and/or precursors not suitable for the prevailing climatic
or seasonal conditions, Generation of fume not forming part of explosives and its precursors
qualification criteria i.e. Chemical formulation of explosives mixtures and precursors not
checked for quantity and make up of fume under varied field conditions before releasing into
the industry.

These problems can be overcome by ensuring that the explosive which is supplied to the
customer is as per their requirements and also the in process parameters had to be checked
properly so as to minimize the error in the final product quality, also the finished product
should be also checked for all the parameters such as viscosities, density, critical diameter
also for the gel condition (i.e. weather the gel is properly cross linked or not). This will gives
us the information regarding the product quality and also minimizes the chance of emission
of NOx.

The Emission of NOx is also because of the oil leakages because of the faulty drilling
machines and the equipments used before the blasting operation. The diameter of the hole
also affects the emissions or generation of toxic gases. The type of rock and the soil were the
basting is performed is also one of the most important reason for the emission of blast fumes
from the open cast mines.
The explosives which are going to be used for the surface blasting should be properly
selected so as to minimize the chance of partial blast also the care should be taken so as to
avoid the contact of the sample with the water which will increase the critical diameter of the
explosive and because of this the explosive may not blast completely and may result in the
generation of lot of NOx gasses.

The loading and sleeping time of the Explosive should be properly selected or planned this
will decrease the chance of breakdown of the explosive material as their will be less contact
between the explosive material and water.
The equipment used for the drilling the blast hole should be maintained properly, because if
there is any leakage of oil or other fluids in the blast hole then it may come in contact with
the explosive and can cause the emission of the NOx.

From the above explanations it can be observed that the fumes can be controlled if the proper
precautions are taken.

2.2. Hazards of NOx Emissions:-

The NOx is the mixture of gases that are composed of nitrogen and oxygen. The two most
toxic of these gases are nitrogen dioxide and nitric oxide. These gases when released in the
air or comes in contact with the water forms nitric oxides and nitric acid and react with
alkalies to form nitrates and nitrites.
The Nitrogen dioxide is the most hazardous component of the NOx emission. The over
Exposure to Nitrogen oxides can cause following health hazards to the human body:-

2.2.1 Low Level exposure can:-

2.2.1.1 Irritate the eyes, nose, throat and lungs;
2.2.1.2 Cause coughing and shortness of breath;
2.2.1.3 Cause nosebleeds and headaches;
2.2.1.4 Cause tiredness and nausea;
2.2.1.5 Cause a build up of fluid in the lungs (which may take 1-2 days)
2.2.1.6 Cause acquired or type II methemoglobinemia.
2.2.2Exposure to high concentrations can:
2.2.2.1Swelling of tissues in the throat, and upper respiratory tract;
2.2.2.2 Cause rapid burning to exposed body parts (eyes, nose, throat, lungs);
2.2.2.3 Reduced oxygenation of body tissues
2.2.2.4 Muscle spasms;
2.2.2.5 A build up of fluid in the lungs (pulmonary oedema)
2.2.2.6 Death

3. PRECAUTIONS TO BE TAKEN TO PROTECT THE PERSONNEL FROM THE

HARMFUL EFFECT OF THE NOX:
There are a number of ways to protect workers and neighbours from toxic fumes produced by
blasting operations such as:-
3.1. Minimize the quantity of toxic fumes produced. This can be done by suitably designing
the formulation of the explosives.
3.2. Determine where the fumes may go so workers and neighbours may be moved out of the
way. This can be achieved by position the worker away from the possible path of the fumes.
3.3. Prevent the fumes from moving towards workers and neighbours.
3.4. Monitor the air near workers and neighbours so they can be relocated if fumes appear,
3.5. Ventilating structures or confined spaces until CO falls below a hazardous concentration.

4. CONCLUSION:-
The major cause of the production of NOx fumes after the blast is because of the improper
design of the formulation of the explosives and also because of the improper selection of the
explosive, side conditions and also some times because of manual errors. The emission of the
NOx can be minimized by suitably designing the formulation, properly selecting the
explosives and also the site conditions and equipments used for the pre blast preprations.