1. Is it a chemical or biological role or is it both ?
The role of Phosphate and Phosphate mining wastes in controlling ARD and AMD.
Is it a chemical or biological role or is it both ?
Invited by
West Virginia Mine Drainage Task Force Symposium
Morgantown , March 2011
M. Kalin and W. N. Wheeler
Boojum Research Ltd
Toronto, Canada
Boojum Research LTD years of Ecological Engineering

2. Margarete Kalin/Boojum Research LTD
President and founder of Boojum Research LTD
Adjunct professor at U of Toronto, Ryerson University, U of Windsor, Queen’s Univeristy , Kingston
QEP with the Institute of Environmental Practice and Senior Ecologist with the American Ecological Society.
has written and presented more than 100 scientific papers, many book chapters and more than 100 technical reports
has applied the technology to effluent streams from coal, uranium, base metal and precious metals in North and South America as well as Europe.
RECIPIENT OF THE:
Noranda Award for Outstanding Achievement in the Field of Land Reclamation
Teck-Cominco Environmental Award
Distinguished Lecturer for the Canadian Institute of Mining.
Boojum Research LTD years of Ecological Engineering

3. No patents – Natural processes : Virtual Library
Company is 29 years old, with contracts worldwide.
Canadian contracts only shown

4. ECOLOGICAL ENGINEERING
aims to practically and beneficially apply knowledge of how ecological systems operate on the mineral and rocks surfaces within these landforms
it utilizes the dynamics of well-adapted organisms within
MWWMA – no extra space needed
identifies those factors blocking the way to ecosystem growth
targets those locations within the MWWMA (sediment, rock surfaces or the AMD water) with applications of essential elements to promote growth (e.g. organic carbon, phosphate etc.)
move the it is
Boojum Research LTD years of Ecological Engineering

5. Gallionella ferruginea with ochreous deposits of bog iron.
These ecosystems are living landforms – they change with time
BIOGEOCHEMISTRY
Geomicrobiology
Microbial
Ecology
Biogeochemistry
1838
Ehrenberg
Gallionella ferruginea with ochreous deposits of bog iron.
1887
Winogradsky Beggiatoa oxidation H2S to elemental sulfur; Leptothrix ochracea oxidation of FeCO3 to ferric oxid
1919
Harder
microbial iron oxidation and precipitation in iron sedimentary deposits.
Stutzer (1911)
Vernadsky ( )
Geomicrobiology has a long history- and they dominate the MWWMA ecosystem

6. Mineral Surfaces: The Site of the Problem and the Solution
Oxidation of sulphide particles in tailings, waste-rock piles, underground mine workings and open pit walls
Limited by the transport of oxygen
Convection, advection or diffusion to the mineral surface
Bacterial biofilm activity – BOTH OXIDATIVE AND REDUCTIVE – CHANGE THE HABITAT / ENVIRONMENT

7. Scale diagram of typical bacteria size compared to the surface roughness
Nutrients need to be added, NOT to the water, BUT to the rock surfaces and it has to stick to the rock in the oxidation pit

8. Members of this Task force did leading work with tests of phosphate material

9. Results from 5 Soxhlet leaching cycles – Appendix 1pH Fe S
Acidity
Cond
NO PHOSPHATE*
Cycle 1
2.0
1100
3000
360
14.20
Cycle 2
2.6
170
400 38
2.70
Cycle 3
2.8 55
140 29
1.66
Amendments all types including North Carolina phosphate
min – max
Cycle 1**
1.8 – 2.3
436 – 1206
150 – 390
7.2 – 13.75
2.8 – 3.6
25 – 119
190 – 493
8 – 32
1.3 – 2.36
2.8 – 3.5
8 – 63
7 - 28
1.0 – 1.4
My conclusion; Internal precipitation took place
* Calculated average N=3
** N= 24, each amendment all application rates N=3

10. Field experiment Fill #2 - 366 Tons shale/coal (parting)
Fill # Tons shale/coal l with 1.14 tons of apatite rock
Fill # Tons shale/coal with .55 tons of apatite rock
Results were good – but did not make sense – so let‘s think what went wrong!

11. Acid Mine drainage treatment: Phosphate Technology- the chemical Phosphate role
P and Fe cycling are closely linked
P concentrations (e.g. for organisms) are generally very low
P is sequestered as co-precipitates with Fe hydroxides (oxic conditions)
P forms metal salts (anoxic conditions)
P is bound by organics (e.g. humic substances in muskeg)
P may absorb to pyrite (source of AMD) surfaces and inhibit acid generation

12. How did it start? A customer requested that something should be done to reduce oxidation rather than waiting for it occur!
The Northern Miner Magazine Sept Oct reported on the cessation leaching of Cu from a dump in B.C.
Sample obtained in 1992
Boojum Research LTD years of Ecological Engineering

13. The key questions are :
How do we get NPR to the mineral surface or to the place where the AMD is generated?
AND
It has to be economic and practical
It has to be suistainable – lasting for ever
It has to be general – i.e. work in all types of wastes

14. Relating the Scale of the Observations
Phosphate Rock
Waste Rock
NPR Code 48
4 mm to < 0.04 mm
150 mm

15. Boojum Research LTD - 25 years of Ecological Engineering

16. B- zone waste rock pile in distance with muskeg area in front
Boojum Research LTD years of Ecological Engineering

17. Distribution of measured elements comprising 10% of a Waste Rock Pile
B-zone waste rock pile
As (0.07%)
S (0.29%)
Fe (10%)
LOAD IN SEEPAGES As Fe S
Annual Load
% Leached from pile
%/year
0.26
0.0003
0.65
Years to exhaustion
year
378
322
153
Maximum elemental concentrations in Rock and Secondary Precipitate As Fe S
Whole Rock
mg.g-1
2.7 43
1.5
n=97
WRP-P Precipitate
242
206
7.2
n=1
Boojum Research LTD years of Ecological Engineering

18. We had to work in the field first – it has to work there, so we set up large field tests with Texas Gulf Natural Phosphate Rock – Train cars full of the stuff came to Northern Ontario and Quebec
In uranium tailings
In phyrrotite tailings ( Cu , Ni )
In coal, coarse waste rock
in polymetallic concentate spills
In sulphidic waste rock ( Cu , Zn )

19. Autopsy section overview
Piles 1 to 4
Lime compacted etc
Pile 5 NPR

20. Tailings Surface Cover Development through Integration of Reactive Phosphate and Organic Matter (PHITO)
Boojum Research LTD years of Ecological Engineering

21. integrate nutrients, precipitation agents and NPR below the roots, then grow organics
Boojum Research LTD years of Ecological Engineering

22. Heterotroph Oxygen Requirements
Stanrock: Horse Manure and Natural Phosphate Rock
1995
Heterotroph Oxygen Requirements
Heterotrophs counted fresh tailings: 107/g
Populations oxygen requirement: µL/g
Oxygen present in fresh tailings: < 20 µL/g
Boojum Research LTD years of Ecological Engineering

23. Only practical long term tests in mining wastes in the field can provide evidence of the validity of the assumptions
Tests NPR additions to tailings and conc. spill
2- 85 % sulphide
left in field years
monitor the pore water metal acidity
TAILINGS AREA –
Inco: 2700m2;
Stanrock:432 m2
Test NPR additions to waste rock
4-15 % sulphide
left outdoors 2.7 years
monitor the effluent metal acidity
Monitoring 1.8
Boojum Research LTD years of Ecological Engineering

24. Results of the waste rock drums
Boojum Research LTD years of Ecological Engineering

25. pH profile for low pyrite
Stable layer
Unstable layer
no matter what amount of pyrite – acid rock drainage is with you !
Boojum Research LTD years of Ecological Engineering

26. Pore water results : Control NO NPR and NPR additions
If sulphide oxidation can be reduced - the process has to be similar in a large variety of mining wastes:
Uranium
Pyhrrotite
Polymetalic
Waste rock
Elements (mg.L-1)
Control
NPR
N=1
N=2
N=3
N=6 Fe 18
0.01 43
0.1
1053
0.02
3.77
0.32 P
0.03
0.05
0.22
6.9
0.16
0.04
0.20
0.13 S
630
510
4460
1060
3020
500
126
123 pH
2.67
6.75
3.06
3.84
2.59
5.40
4.06
6.09
Acidity (mgCaCO3 .L-1)
656 39
6715
1090
5544 87
257 76
Pore water results : Control NO NPR and NPR additions

27. Williamson and Rumstidt . 1994
OXIDATION RATES
Williamson and Rumstidt
r = (±0.86). Eh12.93(±1.04). pH1.0(±0.29) (1)
log r =-19.71(±0.86) (±1.04)log(Eh) +1.0(±0.29)log(pH)
Boojum Research LTD years of Ecological Engineering

28. The reactant: Phosphate mining wastes or Natural Phosphate Rock
Un-economic for fertilizer production
a sedimentary deposit N. Carolina – Sea shells –Shark teeth (organophosphate)
grain size 4cm to < 0.04 mm
NPR contains 8-12 % P and % Ca (as CaCO3)
16x

29. Taylor mesh conversion and size description for the NPR Code 48 particles
Taylor Mesh Size Used
Range of Particle Diameter (mm)
M.I.T Particle Classification
Percent finer than
Percentage of the total material 6
>3.35
Fine Gravel (44.8%)
90.754%
9.246% 8
55.183%
35.571% 10
Coarse Sand (52.0%)
10.281%
44.902% 14
4.826%
5.455% 20
3.881%
0.944% 28
3.229%
0.652% 35
Medium Sand (2.2%)
2.600%
0.630% 48
1.819%
0.781% 54
1.008%
0.811%
100
Fine Sand (0.7%)
0.736%
0.271%
150
0.400%
0.336%
200
0.270%
0.130%
270
Silt (0.3%)
0.176%
0.094%
325
0.116%
0.060%
400
0.065%
0.051%
<400
<0.038
0.000%

30. WE HAD THE BIOLOGICAL ROLE OF NPR!
NPR is acid-soluble and provides all the nutrients needed for microbial growth
It needs to be in particulate form on the mineral surface to change the environment
We suspect the fine particles made it to the mineral surface
We dissolved NPR in 0.1N sulphuric acid and only a fraction of it dissolved
WE HAD THE BIOLOGICAL ROLE OF NPR! -
MACRONUTRIENTS
P (nucleic acids synthesis, ATP),
K (enzymes activation),
Ca (cells walls and endospores),
MICRONUTRIENTS
Fe (electron transport systems),
Mn, Cu, Ni, Mo, Co and Zn
(components of protein complexes and enzyme activators)
Source :Chapelle, F; (1993 “Ground-Water Microbiology & Geochemistry” John Wiley & Sons, Inc)

31. Scanning Electron Microscopy of Waste Rock Surface (1st Observation)
1995
Boojum Research LTD years of Ecological Engineering

32. Figure 8 - (A) A2 SEM/EDS 2009 (rock 2); (B) A3 SEM/EDS 2004 10
2007
2009
After 3 years of outdoor exposure and 11 years of storage Fe Au S P
AMIRA P933 Report
Boojum Research and U of Toronto
(ongoing research)
Boojum Research LTD years of Ecological Engineering
Figure 8 - (A) A2 SEM/EDS 2009 (rock 2); (B) A3 SEM/EDS 2004 10

33. Mineral Surfaces: The Site of the Problem and the Solution
Waste rock with NPR
Untreated waste rock
Untreated waste rock
Waste rock with NPR

34. Bugs generally cause only trouble, but when fed, they are here to help
Bugs generally cause only trouble, but when fed, they are here to help! A mining research group confirmed the presence of a biofilm on rocks from our experiment in 2008.
It is presently being tested on other waste rock by the same group.
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