the influence of secondary mineral phase crystallization on antimony and arsenic mobility in mine

202 Pages·2017·20.28 MB·English

THE INFLUENCE OF SECONDARY MINERAL PHASE
CRYSTALLIZATION ON ANTIMONY AND ARSENIC
MOBILITY IN MINE DRAINAGE

by

Anežka Borčinová Radková

A thesis submitted to the Department of Geological Sciences & Geological Engineering
In conformity with the requirements for
the Degree of Doctor of Philosophy

Queen’s University
Kingston, Ontario, Canada

May 2017

Copyright © by Anežka Borčinová Radková, 2017
Abstract
Mine waste containing high concentrations of the potentially toxic metalloids antimony (Sb) and arsenic
(As) poses a risk for the natural environment since they are toxic to various organisms. To assess this risk,
it is necessary to understand the role of mineralogy, particularly the influences of solubility and variable
chemical composition of minerals.
The sites selected for this study allow an insight into the Sb behaviour in three different systems: freshly
deposited stibnite-containing tailings at Beaverbrook Sb mine (Newfoundland), historical mine waste at
Špania Dolina-Piesky (Slovakia) where tetrahedrite is the main Sb host, and several historical Sb deposits
in Slovakia where the Sb association with colloids was investigated. Water analyses using ICP-AS-OS,
HG -AAS were combined with mineralogical analyses conducted using a combination of SEM, EMPA,
MLA and synchrotron-based μXRD, μXRF and μXANES (see the list of abbreviations).
The study of tetrahedrite weathering reveals that after being released from primary tetrahedrite, Sb
becomes a part of a structure of secondary Sb minerals tripuhyite and pyrochlore which are stable in near-
surface conditions, whereas As and Cu are contained in µXRD-amorphous phase. It is concluded that Sb
is not very mobile when tetrahedrite is weathering under oxidizing, near-neutral conditions.
At Beaverbrook, Sb is rapidly released from stibnite in tailings deposits to the pore water in an oxic
environment where it transforms to highest oxidation state Sb5+. Arsenopyrite oxidizes less rapidly, and
the formation of oxidation rims contributes to its slower dissolution. The formation of less soluble Sb-Fe
secondary phases, and formation and dissolution of easily soluble brandholzite contribute to Sb cycling in
the environment of freshly deposited tailings.
In mine drainage from several historical mine sites, it was determined that colloids influence As mobility
more than Sb mobility. At the sites where As is the main contaminant, abundant Fe-As-Si-O colloids
ii
were detected on the surface of 0.01 µm filters. Only very high Sb concentration (above 6600 µg/L)
promoted precipitation of low amounts of Fe-Sb-Si-O±S colloids.
Secondary Sb minerals with different stability are formed in mine waste environment. Understanding the
conditions of their formation and their characteristics allow the prediction of potential environmental
issues.

iii
Co-Authorship
This dissertation thesis includes three manuscripts for journal publication. Chapter 2
“Mineralogical controls on antimony and arsenic mobility during tetrahedrite-tennantite weathering at
historic mine sites Špania Dolina-Piesky and Ľubietová-Svätodušná, Slovakia” was submitted to the
American Mineralogist on October 26th, 2015 and was peer reviewed and published in May 2017. The co-
authors are Heather Jamieson, Queen’s University; Bronislava Lalinská-Voleková, Natural History
Museum, Slovakia; Juraj Majzlan, Friedrich-Schiller University, Germany; Martin Števko, Comenius
University, Slovakia and Martin Chovan, University of Ostrava, Czech Republic. Martin Števko; Juraj
Majzlan and Martin Chovan provided part of the samples and their description and analyzed them by
electron microprobe. Heather Jamieson acted as a fieldwork mentor and together with Bronislava
Lalinská-Voleková acted as a supervisors and advisors for synchrotron analyses and µXRD data analyses.
All the coauthors provided guidance and reviewed the work.
Chapter 3 “The control on Sb mobility during the early stages of stibnite weathering in tailings at
Beaverbrook antimony deposit, Newfoundland” is a manuscript for submission as a journal publication to
the Applied Geochemistry. The coauthors are Heather Jamieson, Queen’s University and Kate Campbell,
United States Geological Survey. Heather Jamieson acted as a supervisor of the project, provided
fieldwork guidance; and Kate Campbell was a field work assistant and performed analytical results of
water (including Sb, As and Fe speciation). Both coauthors provided review and guidance.
Chapter 4 entitled: “Geochemical characterization of colloids from mine drainage waters and
their role in Sb and As transport” is a chapter anticipated to be submitted to Mine Water and
Environment. The coauthors are Heather Jamieson who provided guidance, field work assistance and
review and Bronislava Lalinská-Voleková who performed part of the colloid and water sampling.
iv
Acknowledgements
My very special thanks belong to my supervisor Heather Jamieson. Thank you for your guidance,
for giving me encouragement, sharing your knowledge, for your patience and for keeping an excitement
about this project. It was an honour and pleasure to work under your supervision.
I would like to thank to former and recent members of Jamieson research group. Thank you for
your friendship, support during hard times, for always finding time to discuss mysteries of geochemistry
and for all the great laughs we had. You made my time at Queen’s #krasny.
Bryn Kimball and Kate Campbell, you were the best field assistants I could wish for. Thank you
for passing on your skills and for keeping good mood during several mosquitos’ attacks.
I would like to thank Agatha Dobosz and Brian Joy for helping to analyze my samples and not
loosing hope in getting the results, despite of the challenges samples of mine waste brought. Thank you,
Robert Gordon and Zou Finfrock for your assistance during long days and nights at synchrotron.
Thank you Bronislava Lalinská-Voleková, Martin Chovan, Juraj Majzlan and Martin Števko for your
guidance and assistance during the fieldwork in Slovakia. You all are a great inspiration for me as
scientists.
This project would not be possible without financial support from Natural Science and
Engineering Research Council of Canada Discovery Grant to Heather Jamieson, from the Slovak
Research and Development Agency under the contract No. APVV-0663-10, Travel Award from Society
of Economic Geologists and Queen’s University Dean's Travel Grant for Doctoral Field Research.
Finally, I would like to thank my friends, family and especially my husband Martin for their love
and never losing confidence in me. Thank you for always being there for me.
v
Statement of Originality
I hereby certify that all the work described within this thesis is the original work of the author. Any
published (or unpublished) ideas and/or techniques from the work of others are fully acknowledged in
accordance with the standard referencing practices.
Anezka Borcinova Radkova
May 2017
vi
Table of Contents
Abstract ................................................................................................................................................... ii
Co-Authorship ........................................................................................................................................ iv
Acknowledgements ................................................................................................................................. v
List of Figures ......................................................................................................................................... x
List of Tables ........................................................................................................................................ xii
Chapter 1 Introduction ............................................................................................................................. 1
1.1 Research objectives........................................................................................................................ 1
1.2 Background and research motivation .............................................................................................. 3
1.3 Thesis organisation ........................................................................................................................ 8
1.4 References ..................................................................................................................................... 9
Chapter 2 Mineralogical controls on antimony and arsenic mobility during tetrahedrite-tennantite
weathering at historic mine sites Špania Dolina-Piesky and Ľubietová-Svätodušná, Slovakia ................. 12
2.1 Abstract ....................................................................................................................................... 12
2.2 Introduction ................................................................................................................................. 13
2.3 Site description ............................................................................................................................ 15
2.4 Materials and Methods ................................................................................................................. 19
2.4.1 Sample collection .................................................................................................................. 19
2.4.2 Electron microprobe analysis (EPMA) .................................................................................. 19
2.4.3 Synchrotron micro-analysis ................................................................................................... 19
2.5 Results and Discussion................................................................................................................. 21
2.5.1 Chemical composition of primary tetrahedrite-tennantite minerals ......................................... 21
2.5.2 Tetrahedrite weathering products ........................................................................................... 23
2.5.2.1 X-ray amorphous oxidation products. ................................................................................. 26
2.5.3 Chemical composition and mineralogy of tennantite oxidation products ................................ 37
2.6 Implications ................................................................................................................................. 40
2.7 References ................................................................................................................................... 41
Chapter 3 The Controls on Sb Mobility During the Early Stages of Stibnite Weathering in Tailings at the
Beaverbrook Antimony Deposit, Newfoundland .................................................................................... 46
3.1 Abstract ....................................................................................................................................... 46
3.2 Introduction ................................................................................................................................. 48
3.2.1 Geological setting ................................................................................................................. 51
3.2.2 History of mining .................................................................................................................. 52
3.3 Methods ....................................................................................................................................... 54
3.3.1 Tailings and Fe precipitates ................................................................................................... 54
vii
3.3.2 Drainage water ...................................................................................................................... 55
3.4 RESULTS AND DISCUSSION ................................................................................................... 57
3.4.1 Water system at Beaverbrook ................................................................................................ 57
3.4.2 Mine drainage chemistry ....................................................................................................... 57
3.4.3 Sb and As in drainage water .................................................................................................. 61
3.4.4 Tailings sediment - bulk characterization ............................................................................... 66
3.4.5 Primary gangue minerals and sulphides ................................................................................. 66
3.4.6 Secondary minerals with Sb .................................................................................................. 68
3.4.7 Modal mineralogy and distribution of Sb in top layers of tailings ........................................... 72
3.4.8 Fe precipitates ....................................................................................................................... 75
3.4.9 Thermodynamic stability of Sb minerals: The link between mineralogy and water chemistry –
PHREEQC results.......................................................................................................................... 76
3.5 Concluding remarks ..................................................................................................................... 80
3.6 References ................................................................................................................................... 83
Chapter 4 Geochemical Characterization of Colloids from Mine Drainage Waters Influenced by Sb
Mining, and Their Role in Sb and As Transport. .................................................................................... 87
4.1 Abstract ....................................................................................................................................... 87
4.2 Introduction ................................................................................................................................. 89
4.2.1 Field sites .............................................................................................................................. 93
4.3 Methods ....................................................................................................................................... 98
4.3.1 Colloids sampling and water analyses .................................................................................... 98
4.3.2 Scanning Electron Microscopy (SEM) ................................................................................... 98
4.3.3 Synchrotron analyses............................................................................................................. 99
4.4 Results ....................................................................................................................................... 100
4.4.1 Sb, As and Fe concentrations in mine waters filtered <0.45 µm and ultrafiltered samples..... 100
4.4.2 The occurrence and the chemical composition of colloids – SEM analyses .......................... 109
4.5 Discussion ................................................................................................................................. 114
4.5.1 Antimony and arsenic association with colloids of Fe oxyhydroxides .................................. 115
4.5.2 Comparison of VIVA cell and Stirred cell ........................................................................... 117
4.6 Conclusions ............................................................................................................................... 119
4.7 References ................................................................................................................................. 120
Chapter 5 Conclucions and Recommendations for Further Work ......................................................... 125
5.1 Tetrahedrite weathering products ............................................................................................... 125
5.2 The control on Sb mobility during the early stages of stibnite weathering in tailings ................... 126
viii
5.3 Geochemical characterization of colloids from mine drainage waters and their role in Sb and As
transport .......................................................................................................................................... 128
5.4 Key results ................................................................................................................................. 129
5.5 Recommendations for further research ....................................................................................... 130
5.6 References ................................................................................................................................. 132
Appendix A .Additional data to Chapter 2 ............................................................................................... 133
Appendix B .Additional data to Chapter 3 ............................................................................................... 159
ix
List of Figures
Figure 2.1 Generalized geological map and a photograph of waste rock pile of Špania Dolina area,
showing the location of the historical waste rock piles with bedrock geology ......................................... 16
Figure 2.2 Geological map of Ľubietová area ......................................................................................... 17
Figure 2.3 Olive-green masses of oxidation products with relics of the primary tetrahedritefrom the
oxidation zone of Špania Dolina-Piesky deposit. .................................................................................... 23
Figure 2.4 BSE images of tetrahedrite weathering products .................................................................... 25
Figure 2.5 Elements variations in X-ray amorphous phases resulting from tetrahedrite weathering ......... 27
Figure 2.6 Element variations in amorphous phases chemically similar to roméite, pure roméite and a
nanocrystalline mixture of tripuhyite and roméite .................................................................................. 31
Figure 2.7 A: Sb XANES spectra of the model compounds and of the tripuhyite-roméite mixture. ......... 35
Figure 2.8 Distribution of Sb, As, Cu and Fe in the ttd oxidation products.............................................. 36
Figure 2.9 Sb-As-Fe plot of the secondary minerals identified................................................................ 37
Figure 2.10 BSE image of tennantite and X-ray amorphous oxidation products.. .................................... 38
Figure 3.1 Beaverbrook mine location and geologic map with a location of the two tailing ponds. ......... 52
Figure 3.2. Aerial photograph, water sampling locations, pH, Sb, As and Fe concentration in water at
Beaverbrook mine site . ......................................................................................................................... 60
Figure 3.3: pe–pH diagram for the Sb–O–H system and As–O–H system with measurements of mine
drainage and pore water at Beaverbrook mine site.................................................................................. 64
Figure 3.4. Primary sulphide minerals in top layers of tailings impoundments ........................................ 68
Figure 3.5 Three types of secondary minerals with Fe, Sb and As in Beaverbrook tailings and As-Fe-Sb
plot of the composition of the secondary phases ..................................................................................... 71
Figure 3.6 Brandholzite tabular crystals from Beaverbrook tailings. ....................................................... 72
Figure 3.7 Sb mass distribution in Sb containing phases in selected samples from vadose and saturated
zones of Tailings 1 and Tailings 2 as determined by SEM-MLA. ........................................................... 74
Figure 3.8 BSE images of Fe ocherous precipitates in tailings drainage water, Beaverbrook Sb mine,
Newfoundland. ...................................................................................................................................... 76
Figure 3.9 PHREEQC modeling results for surface (blue) and pore water (red) at Beaverbrook ............. 81
Figure 4.1 Particles and their respective size ranges ............................................................................... 91
Figure 4.2 Common charges of natural colloids ..................................................................................... 93
Figure 4.3 Location of the colloids sampling sites - abandoned mines in Slovakia. ................................. 95
Figure 4.4 Sampling sites of mine drainage water and colloids ............................................................... 99
Figure 4.5 The flow chart of water filtration and analyses. ................................................................... 102
Figure 4.6 Fe, As and Sb concentration in samples form Agnes adit outflow at Poproč sampled in 2013,
2015 and 2016. .................................................................................................................................... 105
Figure 4.7 Fe, As and S concentration in samples from Pezinok tailings drainage sampled in January 2016
and August 2016. ................................................................................................................................ 106
Figure 4.8 Fe, As and S concentration in samples form Dúbrava (Samuel adit outflow) in 2013, 2015 and
2016. ................................................................................................................................................... 108
Figure 4.9 Fe, As and S concentration in samples from Beaverbrook (2015). ....................................... 109
Figure 4.10 Fe, As and S concentration in samples from Čučma (2016) and Medzibrod (2015). ........... 111
Figure 4.11 SEM images and chemical analysis of colloids from Agnes adit outflow collected by Stirred
cell in 2013,2015 and 2016 and VIVA cell in 2016. ............................................................................. 113
Figure 4.12 SEM image and representative EDS spectra of colloids from Pezinok site collected by Stirred
cell in January and August 2016. ......................................................................................................... 114
Figure 4.13 SEM image and chemical composition of colloids from Beaverbrook and Dúbrava. .......... 115
x