AMMONIUM NITRATE IN MINE WATER

ACASESTUDY
CARLOS AGREDA Ph.D*
PERUVIAN MINING RESEARCH COMPANY (PEMIRECO)
Lima - Perti

JiBSTRACT

In the present article a case study of ammonium nitrate in

mine water is briefly analized and discussed.

Causes of mine water pollution from AN are very well

identified and emphasized.

Some preventative measures, as well as, some methods of

monitoring and control to minimize, mitigate and/or avoid
mine water pollution are recommended.

* BLASTING Consultant, National University of Engineering

Profesor. PEMIRECO's Executive President.

Figures, tables and references follow the text.

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 117 1 of 13
1.0 Introduction

It is well known that environmental impacts produced by

the rock blasting unit of a mining operation are
multiple.

The most identified, monitored, evaluated, and

controlled are the following: dust, poisonous gases, fly
rock, vibration, air pressure and noise.

In this paper, a special study of mine water pollution

produced by high levels of nitrogen in the form of
nitrates (NO,) and ammonia (NH,) is presented.

2.0 Problem Formulation

This case study was carried out in an underground minig

operation in Canada.
It was detected in the mining operation that the mine
liquid effluents contained high levels of nitrogen in
the form of nitrates (NO,) and ammonia (NH,). To solve
this problem, the contaminating sources had to be
identified, and then these sources had to be minimized,
mitigated and/or avoided.
Figure 1 schematically shows the principal points (in-
puts) of clean water into the mine, the water collection
points and the mine water exit mechanism (pumping-
station).

.
3.0 Idantification of the Water PO&&&&~ Contmt

Several lab and field tests were conducted to deduct

that the principal mine water contaminant was the AN/F0
used in the blasting unit mining operation.
Copyright © 2000 International Society of Explosives Engineers
1999G Volume 1 - Ammonium Nitrate In Mine Water - P 118 2 of 13
 Tables I and II show the results of the analyses of some
mine water samples.

4.0 How the Mine Water Was Beincr Polluted

To carry out the rock blasting operations in this

underground minining operation, AN/F0 dry blasting
agent was being used; for wet blast holes some slurries
and emulsions were used but in less quantities. It must
be kept in mind that the AN/F0 composition is almost
totally made up of nitrates (NO,) and ammonia (NH,).

Therefore, the disolution of small quantities of AN/F0

might produce high levels of nitrates and ammonia in the
mine liquid effluents.

Then the conclusion was reached that there was no other

sources of nitrates in the underground liquid effluents
other than the blasting agents used in rock blasting.

5.0 Nain Sources of Mine Liuuid Effluents Contamination

The main sources of contamination were the following:

Spillage in handling of bags.
Blow back from pheumatic loading.
Wastage of excess material after loading was completed.
Misfires which had to be washed out, etc. etc.

6.0 Main Factors Causinu Blow Back, Fall and Spillage

If the blast holes are not properly loaded with AN/FO,

then the required density is not obtained, and the
worker's normal practice is to throw away the last
loaded part and re-load the blast hole.
Copyright © 2000 International Society of Explosives Engineers
1999G Volume 1 - Ammonium Nitrate In Mine Water - P 119 3 of 13
 The blast holes from which water is pumped before being
loaded (the water stays on the floor of the mine and the
AN/F0 falling to the floor is dissolved by this water).

Improper air pressure in the pneumatic loader (too high,

which causes unnecessary blow back).

Spillage of AN/F0 onto the floor of the mine from the

hose of the pneumatic loader after loading is completed.

Spillaae
This is due to:

Broken bags
Overflow at the top of the loader, when dumping
bags into the loader.
Dumped bags.

7.0 Fnerav Given Bv The AN/F0 Detonation

When AN/F0 detonates, the atoms of this explosive

mixture will take part in competitive reactions of
gases. The resultant products will depend upon the
reactant proportions present of the equilibrium
constants for the gases reaction and temperature.

The quantity of ammonia (NH,), nitric oxide (NO), and

nitrogen dioxide (NO,) produced will mainly depend upon
the ammonium nitrate (AN) relation to the No. 2 fuel oil
(FO), in the commercial explosive mixture called AN/F0
as well as the confinement.

The given energy, when detonating AN/FO, can be

calculated for different AN and FO ratios.

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 120 4 of 13
 The maximum energy obtained when AN/F0 is blasted occurs
when all oxygen is used by the combustibles to give CO,,
H2G and NZ.

It is important to determine the correct proportion AN

and FO should be mixed to obtain the maximum energy at
detonation and, above all, to minimize the poisonous
gases produced by the AN/F0 detonation which will
contaminate the mining environment.

8.0 Chemical Fractions Of me AN/F0 For Different Ratios Of

Its Inuredients

AN/FO=92/8(0xygen deffect 1. 0, =-)

2N0,NH,+CH2 4 5H,OtCOtZN,+761 Kcal/Kg
AN/FO=94.4/5.6 (Balanced Oxygen :. 0,--O)
3NO,NH,tCH, + 7H,OtCO,t3N,+900 Kcal/Kg
AN/FO=96.4/3.6 (Oxygen excess.'. 0, :. = +)
5NH,NH,tCH2 + 11 H,O t CO,t2NOt2N,t550 k'cal/k:y.

Figure 2 shows the curve obtained by plotting (NH,) vs.

(NO,) corresponding to No. 1 test.

Figure 3 shows the curve obtained by plotting (NH,) vs.

(NO,) corresponding to No. 2 test.

9.0 Survev of amnonium nitrate levels in mime water

After initial work indicated high levels of ammonia

(NH,) and nitrate (NOJ) in mine water, the research
departament in conjuntion with a request from the mining
departament conducted a level by level survey for these
contaminants .

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 121 5 of 13
The results of these two tests are shown in tables I and
II respectively.

9.1. Procedure

Taking into account these results, the 600 level of the

mine was chosen for further test work because of the
relatively consistant high ammonia level and the small
number of working places.

The water flowing from the box holes of the working

places on 600 was analyzed and recorded in tables I and
II with the description of the work in that area. The
data indicated that the largest contributors of ammonia
(NH,) were the areas being blasted.

9.2 Results

The results of these two tests are contained in tables

I and II and plotted in figures 2 and 3 respectively.

9.3 AN/F0 losses

From conversations with underground personnel, it was

indicated that a little more than two 50 lb. bags of
AN/F0 were required to load an 8 ft raise round. The
majority of a third bag was discarded. This wastage
constitutes one bag in six or approximateley 16%.
Similar sources of spillage were also noted and, these
combined with water damage to stored AN/FO, an estimated
loss of lo-15% of total daily usage would be the case.
Based on the analytical data and mine water tonnage, the
daily input to the pumping station of ammonium nitrate
was approximately 700 lb. Or 13.4% of the daily AN/F0
used.
Copyright © 2000 International Society of Explosives Engineers
1999G Volume 1 - Ammonium Nitrate In Mine Water - P 122 6 of 13
10.0 Discussion

10.1 AN/F0 Handling Procedures

In the mine where this case study was carried out, AN/F0
blasting agent was used extensively in the blasting
operation. The AN/F0 was transported in 50 lb. bags and
store in underground powder magazines. The ml lers
carried the bags to their work-L:-:g places where the AN/F0
wa_ pneumatically loaded into the blast holes.

10.2 High nitrate level

Several investigators working for dyno nobel Inc. state

that al least ninety nine percent (99%) of the AN/F0 in
the blast hole will descompose completely during
detonation.

The Ammonium Nitrate/Fuel Oil mixture descomposes

according to the following formulae:

NO, NH, _) 2N, t 4H,O t 0,

And 'at lower heat:

NO, NH, + N,O t ZH,O

Observing the equations shown above, it can be seen that

free ammonia (NH,) is never produced, but the gases
nitrogen (N), oxigen (0) and nitrous oxide is released.
The nitrous ox.yde along, with other gases is swept out
of the area by ventilating air. However, due to the
high solubiiity of nitrous oxide, and the presence of
cold moist air, water droplets containing large amounts
Copyright © 2000 International Society of Explosives Engineers
1999G Volume 1 - Ammonium Nitrate In Mine Water - P 123 7 of 13
 of nitrate are formed on nearby rock.

Therefore, the mine water should contain a nitrate level

hiyher than the stoichiometric prediction for a water
solution of ammonium nitrate. The nitrate level was
found to be 4.6 times greater than the ammonia level
while the ratio was: 3.6:1 in an AN/F0 water solution.
These are concentrations of nitrates.

From these facts, it can be seen that the ammonia in the

mine water must be due to dissolution of ammonium
nitrate that has been discarded and that the estimate of
the loss IUJ/FO must be based on the ammonia level due to
that additional nitrate level from nitrous oxide.
Obviuosly that the levels found were higher that the
expected quantities produced by the discarded + NO.

11.0 Conclussions and Recumendations

Due to the present mining method, it would be impossible

to completely eliminate the wastage of ammonia nitrate.
However, the loss of 1.700 lb. a day was excessive and
attention was brought to the reduction of losses. The
use of 25 pound bags of AN/FO, along with the 50 lb.
bags helped cut waste. Applying this recommendation, the
losses were reduced by 50%.

The AN/F0 loaders (pressure type) must be kept in proper

conditions, and to show, if possible, that satisfactory
results could be achieved leaving up to 2 ft. of collar.

The use of NONEL detonators was strongly recommended as

a means of reducing misfires.

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 124 8 of 13
Recommendation made to palletise the AN/F0 shipments in
order to reduce handling and subsequent breakage that
was estimated by the mine to be at least 4 bags per day.

A recommendation to replace ammonium nitrate with sodium

nitrate would not represent anything to alleviate a mine
water pollution.

Nitrates cannot be precipitated from mine water.

Nitrate treatment would call for an exchange processes
with would probably not b e cost effective being done.

All partial bags of AN/F0 remaining after the loading of

a blast must be returned to the magazine and used up on
the next blast. No discarding of a partial bag of AN/F0
in the muck pile can be tolerated.

The last 12" to 18" of a blast at the collar must not be

loaded with blasting agents. It only results in being
blown out of the blast hole and show no significance
value in breaking the rock. They were putting AN/F0 into
the mine water unnecessarily and wasting blasting
agents, consequently increasing blasting costs.

Re-instructing operators to try to minimize blow back

when loading. This was not an easy thing to do as it
took considerable practice to get the feel for a proper
stand-off distance with the loading hose. Nevertheless,
it can be done, and will eliminate unnecessary spillage.

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 125 9 of 13
REFERENCES

l.- AGREPA,C.: .'INTR@DUCTION TO EXPLOSIVES TECHNOLOGY",

LIMA-PERU, 1992.

2.- BAUER, A: "EXPLOSIVES TECHNOLGY I", GRADUATE COURSE

CLASS NOTES, MASTER OF SCIENCE PROGRAM IN MINING
ENGINEERING QUEEN'S UNIVERSITY KINGSTON, ONTARIO,
CANADA, Set. 1976.

3.- COOK, M.A.: "THE SCIENCE OF HIGH EXPLOSIVES" N.Y. 1971.

4.- EVANS, W-B-ET AL: "BLENDED AN/F0 BASED EXPLOSIVES"CIM

BULLETIN Set. 1990.

5.- GRUB, R.J.: "SOME FACTORS INFLUENCING THE EXPLOSIVE

PROPERTIES OF AMMONIUM NITRATE - FUEL OIL MIXTURES"
INTERNATIONAL SYMPOSIUM ON MINING RESEARCH, Feb. 1961.

G.- LOOTENS, D.J. ET. Al: "ENVIRONMENTAL MANAGEMENT FOR THE

1990'S"PROCEEDING OF THE SYMPOSIUM HELD DURING THE 1991
SME ANNUAL MEETING.

7.- YANCIK, J.J. : '.MONSANTO BLASTING PRODUCTS AN/F0 MANUAL,

Feb 1970, MONSANTO COMPANY/800 NORTH LINDBERGH BLVD/ST.
LOUIS, MISSOURI.

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 126 10 of 13
 FIGURE 1 - SHOWING THE IN-PUT POINTS
OF CLEAN WATER TO THE UNDERGROUND MINING
OPERATION AS WELL AS THE PUMPING STATION

P@ CONTAINING
HIGHLMLSOF N
lNFORMOF(NO$woH,)

LEGEND
I PUMPING
II, Iz, 13 INPUT OF
CLEAN WATER STATION

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 127 11 of 13
 TABLE I
ANALYTICAL RESULTS
TEST No. 1

IO@
90
so
70
60
50
40
30
20 ! /
10 I
0 , I I I / i’
0 100 200 300 400 NOW-) 500

Fiwre 2: Showing the Curve Obtained Plotting the Results of (NH3) Vs. (N03) Corresponding
to Test No. 1 (Regression Analysis)

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 128 12 of 13
 TABLE II
ANALYTICAL RESULTS
TEST No. 2
SAMPLE N O 3 NH3 RATIO
No (pmm) (pmm) NOaH
1 2-m 57 4.2

I I I

9
8 I 240
270 I 6?
61 I 3.6
4 4 I

2x 330 69 4.11
29 330 61 5.4
AVERAGE 290 63 1.6
~___~_~~_

Figure 3: Showing the Curve Obtained Plotting the Results of (NH3) Vs. (N03) Corresponding
to Test No. 2 (Regression Analysis)

Copyright © 2000 International Society of Explosives Engineers

1999G Volume 1 - Ammonium Nitrate In Mine Water - P 129 13 of 13