Journal of Cleaner Production

Phosphogypsum circular economy considerations:

A critical review from more than 65 storage sites worldwide
--Manuscript Draft--

Manuscript Number: JCLEPRO-D-23-04384R1

Article Type: Review article

Keywords: Phosphogypsum; Circular economy; radioactivity; Cleaner Production

Corresponding Author: Nils Haneklaus

Danube University Krems
AUSTRIA

First Author: Essaid Bilal

Order of Authors: Essaid Bilal

Hajar Bellefqih

Véronique Bourgier

Hamid Mazouz

Delia-Georgeta Dumitraş

Frédéric Bard

Marie Laborde

Jean Pierre Caspar

Bernard Guilhot

Luisa Iatan

Moussa Bounakhla

Măruţa Aurora Iancu

Ştefan Marincea

Meriem Essakhraoui

Binlin Li

Reymar Diwa

Jennyvi D. Ramirez

Yelizaveta Chernysh

Victoriia Chubur

Hynek Roubic

Horst Schmidt

Redouane Beniazza

Carlos Ruiz Cánovas

José Miguel Nieto

Nils Haneklaus

Manuscript Region of Origin: AUSTRIA

Abstract: Nearly 300 million t of phosphogypsum (PG) are produced every year as a byproduct
from phosphate fertilizer production worldwide. Approximately 58% of the PG are
stacked, 28% are discharged in coastal waters and only 14% are further processed.
This critical review provides an overview of the physical-chemical properties of PG
produced from sedimentary and magmatic phosphate ore worldwide using various

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 analytical tools. Results from more than 25 years of work on PG at École des Mines de
Saint-Étienne are presented and critically discussed. In total PG samples from 67
industrial storage sites around the world and PG samples synthesized under different
conditions in the laboratory have been considered. The low radioactivity present in PG
(particularly PG produced from sedimentary phosphate rock) was identified as the
main challenge to using PG as a raw material in construction. Water-soluble and
volatile chemical compounds were identified as the main challenge to environmentally
sound PG management. Although PG does (in most cases) not pose an immediate
threat to the environment the authors recommend processing all PG instead of storing
or disposing it, to eliminate potential long-term risks and utilize a relevant secondary
resource.

Suggested Reviewers: Brahim Bouargane

Ibn Zohr University
[email protected]
Corresponding author of the recent review on phosphogypsum processing that is listed
in the cover letter.

Xiantao Qin
Wuhan Polytechnic University
[email protected]
Corresponding author of the recent review on phosphogypsum processing that is listed
in the cover letter.

Rong Luo
Wuhan University of Technology
[email protected]
Corresponding author of the recent review on phosphogypsum processing that is listed
in the cover letter.

Aziz Boukhair
Chouaib Doukkali University
[email protected]
Professor working on phosphogypsum analysis and processing in Morocco.

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Detailed Response to Reviewers

Reviewers' comments:

Reviewer #1:

Comments to authors:
The authors present an overview of the physical-chemical properties of PG waste around the
world by analyzing more than 60 samples of PG waste. Please find our comments and
remarks below:
- As the number of authors is higher than 6, it is preferable to add "Authors contributions"
section.

Thank you. The comment is much appreciated, and we included “Author contributions” –
Journal of Cleaner Production, calls it “Authors Statement” - in the revised version of the
manuscript.

- Abstract section need revision: Please describe what was done at work, by what
methods, main results and conclusions.
Thank you. We revised the abstract so that methods, main results, and conclusions are now
clearer. Thank you. (We also changed the conclusions to highlight the novel contributions of
this work).
- In the abstract the authors give the following description with regard to PG production:
"Approximately 58% of the PG are stacked, 28% are discharged in coastal waters and only
14% are further processed". How the authors calculate the different amount of PG stacked,
discharged and recycled (58, 28 and 14%)?
Please have a look at these numbers also provided and better explained in Chapter 1
(Introduction). Essentially these are estimates based on published data that we evaluated.
References could not be provided in the Abstracts but are present in the introduction.
- The origin (as countries) of these 67 samples could be declared in the abstract section.
Thank you. The comment is appreciated. There is a word limit on the length of the abstract
though (and it would also be a quite a lengthy list). We made changes to the abstract
following your previous suggestions and are now hitting the word limit. We think that the
previous suggestion to clarify used methods, main results, and conclusions is more
important than a long list of country names and decided not to list the countries in the
abstract. We hope that makes sense.
- Add a reference for this sentence "PG also exists in very small amounts in nature
where it is the result of natural guano processes as they took for instance place in the
Cioclovina Cave located in the Şureanu".
Thank you for spotting that. You are absolutely right, and we added the missing reference.
- I recommend to insert a simplified schema to describe the WPA process (like presented
in this work https://doi.org/10.1007/s41204-021-00125-0)
Thank you. This is again excellent feedback that is much appreciated. We followed the
reviewer’s suggestion and included a simplified flowsheet with mass-balance of the WPA
process in chapter 1 (introduction). Particularly the mass balance we did not see in previous
publications, and we believe that this will really contribute to the quality of this work. Thank
you again for this improvement.
- Table 1: The values could be compared with the concentration of natural radionuclides
in a typical soil.
Thank you. We gave this some thought and could not agree on a typical soil. The idea to
compare the provided values of building materials with a typical soil is not bad. We found it
hard to agree on what a typical soil would be like. We then thought about providing data for
the earth crust. Since neither soil nor earth crust are building materials, we left table 1 as it
was to keep the focus on building materials. We hope this makes sense.
- Please revise the section "Material and methods ", is not informative in that form and it
is too short.
Thank you. We revised the section “Materials and methods” and provided additional
explanation (the revised section is roughly 2 times as long as before) about what was done
here.
- The average PG composition from industrial production (Table 2) should be given as
the following nomenclatures (Groupe 1, 2, 3, 4 and 5).
Thank you for pointing this out. The earlier defined texture and morphology groups (Group 1-
5) cannot directly be linked to the specific WPA processes that are shown in Table 2 since
there are no direct correlations. This was unclear and misleading in the original manuscript,
and we thank the reviewer for the comment. We clarified this now in the revised manuscript.
- Line 282: What is ionic radii??
“Ionic radius, rion, is the radius of a monatomic ion in an ionic crystal structure. Although
neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres
with radii such that the sum of ionic radii of the cation and anion gives the distance between
the ions in a crystal lattice.”
- Section of "circular economy" is not sufficient. Please add more clarifications for this
section.

Thank you. The comment has been well received and we revised the whole section on
circular economy considerations providing an additional figure and analysis on how PG
could contribute to the circular economy. Thank you again for pointing this out. The section
in the original draft was indeed insufficient.
Reviewer #2:
The article titled as "Phosphogypsum circular economy considerations: A critical review from
more than 65 samples collected worldwide" provided an overview of the physical-chemical
properties of PG produced from sedimentary and magmatic phosphate ore worldwide.
Results from more than 25 years of work on PG at École des Mines de Saint-Étienne are
presented.
Following are major results discussed in absttract
1) The low radioactivity present in PG
2) Water-soluble and volatile chemical compounds in PG
3) Authors suggested to process PG instead of storing or disposing it, to eliminate potential
long-term risks and utilize a relevant secondary resource

Comments:
Idea was good to collect PG samples from different locations and analyze it.
Thank you. This is much appreciated.
Too many authors (Essaid Bilal1, Hajar Bellefqih1 , Véronique Bourgier1 , Hamid Mazouz2 ,
Delia-Georgeta Dumitraş3 , Frédéric Bard1 , Marie Laborde1,4, Jean Pierre Caspar5 ,
Bernard Guilhot1 , Luisa Iatan1,6 , Moussa Bounakhla7 , Măruţa Aurora Iancu3 , Ştefan
Marincea3 , Meriem Essakhraoui8
, Binlin Li9 , Reymar R. Diwa10 , Jennyvi D. Ramirez10 , Yelizaveta Chernysh11,12 ,
Viktoriia Chubur11,12 , Hynek Roubík11 , Horst Schmidt13 , Redouane Beniazza14 , Carlos
Ruiz Cánovas 15 , José Miguel Nieto15 , Nils Haneklaus13,16* ). It would be better to add
the individual contribution of each co-author for this publication?
We agree with the reviewer that it is indeed a relatively large list of authors, and we included
an author’s statement in the revised manuscript to clarify the roles and contributions of the
individual authors to this manuscript.
Abstract, Highlights and conclusions are too general, authors should specify the novelty and
key findings of this study. Currently the article is constitutive of general information, which is
already available in literature. Please specify in detail how this study is useful and novel for
the researchers working in this area of research.
Thank you, we agree that the abstract, highlights, and conclusions of the original manuscript
can be improved. We revised abstract, highlights, and conclusions (also other parts) in the
revised manuscript (see track changes) to show the novelty of this work.
Revise highlights and present here the key findings of this study. Which are unique to this
study and not the information which is already know in literature
Thank you. During the revision we made sure that the highlights clearly point to the novelty
of this work.

Avoid clubbing of references in Introduction (Such as " (Kinnunen and 7 Kaksonen 2019;
Tayebi-Khorami et al. 2019; Upadhyay et al. 2021; Cimprich et al. 2022; 8 Luthra et al.
2022)"
Thank you. We revised the manuscript accordingly and avoided clubbing of references.
Add new references where Phosphogypsum has been used for circular economy. This
article is weak in terms of "circular economy" considerations. Although it is one of the most
important aspect of this study
Thank you. The comment has been well received and we revised the whole section on
circular economy considerations providing an additional figure, new references, and analysis
on how PG could contribute to the circular economy. Thank you again for pointing this out.
The section in the original draft was indeed insufficient.

Please revise the layouts of the article by observing the latest published study of this journal.
Currently teher is only 1 para on "Materials and methods" and Results and discussion is
provided in the form of thesis/book chapter and not layout is not good for submitting it as a
research article or review. Authors may take a help of any senior/experienced researcher for
writing it in a appropriate format. Divide section 3 into more subsections/subheadings and
shorten the results and discussion section.
Thank you. The feedback is much appreciated and we studied the latest review articles in
Journal of Cleaner Production ( specifically we studied:
https://doi.org/10.1016/j.jclepro.2023.137084; https://doi.org/10.1016/j.jclepro.2023.137003;
https://doi.org/10.1016/j.jclepro.2023.136973; https://doi.org/10.1016/j.jclepro.2023.137002;
https://doi.org/10.1016/j.jclepro.2023.136942; https://doi.org/10.1016/j.jclepro.2023.136999;
https://doi.org/10.1016/j.jclepro.2023.137054; https://doi.org/10.1016/j.jclepro.2023.137049;
https://doi.org/10.1016/j.jclepro.2023.136845; https://doi.org/10.1016/j.jclepro.2023.136804;
https://doi.org/10.1016/j.jclepro.2023.136815)
In detail we studied the following two review articles that also deal with mineral waste
utilization: https://doi.org/10.1016/j.jclepro.2023.136783;
https://doi.org/10.1016/j.jclepro.2023.136994. In addition, we followed the reviewers
suggestion and consulted with a number (>6) senior/experienced researchers. All of these
researchers have published in Journal of Cleaner Production before. Based on their
suggestions we reviewed and revised the structure of the manuscript. (see track changes in
revised manuscript).

Elaborate more on the conclusions section

Thank you the conclusion section was revised, based on what we learned going through the
previously published articles in Journal of Cleaner Production (previous point) as well as the
new analysis on PG circular economy considerations.
Reviewer #4:
There is no information whether the samples came from current production or alredy stored
waste and whether the time and method of storage had an impact on the results of the tests.
Thank you. This is an extremely valuable comment. Samples were usually dried and then
analyzed shortly after we received them. In general storage of PG samples, even over a
longer period of time should not influence the major element content and minor trace
element content. The reviewer’s comment on this is greatly appreciated though, since we did
not point this out explicitly in the original manuscript, so that this could have raised questions
among the readers. We now included explanation in the revised manuscript that clarifies
these issues.
Has not been determined the potential impact of trace elements on the quality of
manufactured bulding materials, e.g. gypsum board.
Thank you. We revised the relevant section and provided additional references, as well as
additional analysis on the (potential) impact of trace elements on the quality of manufactured
building materials from PG. (See track changes in revised manuscript).
The economics of the project also influenced by use of energy, material and water streams,
as well as the size of the land released as a result of the use of these landfills, not to
mention the aspects that eliminate the negative impact on the environment.

You are right. Thank you for pointing this out. The comment has been well received and we
revised the whole section on circular economy considerations providing an additional figure,
new references, and analysis on how PG could contribute to the circular economy, and thus
freeing more land. Thank you again for pointing this out. The section in the original draft was
indeed insufficient and this comment helped us a lot revising it.
Title Page Click here to access/download;Title Page;230416 Title
Page.docx

Phosphogypsum circular economy considerations:

A critical review from more than 65 storage sites worldwide

Essaid Bilal1, Hajar Bellefqih1, Véronique Bourgier1, Hamid Mazouz2, Delia-Georgeta Dumitraş3, Frédéric Bard1, Marie
Laborde1,4, Jean Pierre Caspar5, Bernard Guilhot1, Luisa Iatan1,6, Moussa Bounakhla7, Măruţa Aurora Iancu3, Ştefan
Marincea3, Meriem Essakhraoui8, Binlin Li9, Reymar R. Diwa10, Jennyvi D. Ramirez10, Yelizaveta Chernysh11,12, Viktoriia
Chubur11,12, Hynek Roubík11, Horst Schmidt13, Redouane Beniazza14, Carlos Ruiz Cánovas15, José Miguel Nieto15, Nils
Haneklaus13,16*
1
École Nationale Supérieure des Mines de Saint Etienne, CNRS UMR EVS, 5600, F42023 Saint Etienne, France
2
OCP Group, Jorf Lasfar, El Jadida, Morocco
3
Institut Géologique de Roumanie, Bucharest, Romania
4
Cepsa Exploracion Y Produccion Slu, Madrid, Spain
5
Division Lafarge Plâtre, Avignon, France
6
Institute of Geodynamics "Sabba S. Stefanescu" of Romanian Academy, Bucharest, Romania
7
Nuclear Centre of Energies, Sciences and Nuclear Techniques (CNESTEN), B.P. 1382, R.P. 10001, Rabat, Morocco
8
Department of Chemisty, Faculty of Science. University Chouaib, Doukka, Morocco
9
College of Economics and Management, Yunnan Agricultural University, Kunming, China
10
Department of Science and Technology – Philippine Nuclear Research Institute (DOST-PNRI), Commonwealth Ave., Diliman, Quezon
City 1101, Philippines
11
Department of Sustainable Technologies, Faculty of Tropical AgriSciences, Czech University of Life Sciences, Prague, 165 00 Prague,
Czech Republic
12
Sumy State University, Rymskogo-Korsakova st. 2, 40007, Sumy, Ukraine
13
Technische Universität Bergakademie Freiberg, Institute of Chemical Technology, Leipziger Straße 29, Freiberg, Germany
14
HTMR-Lab, 43150, Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco
15
University of Huelva, Department of Earth Sciences & Research Center on Natural Resources, Health & the Environment, 21071 Huelva,
Spain
16
Universität für Weiterbildung Krems, Td Lab Sustainable Mineral Resources, Dr.-Karl-Dorrek-Straße 30, 3500 Krems an der Donau,
Austria

*Correspondence: [email protected]

Authors Statement
Conceptualization, Methodology, Writing-Reviewing and Editing: EB; Writing-Reviewing and Editing: HB, NH;
Reviewing and Editing: VB, HM, DGD, FB, ML, JPC, BG, LI, MB, MAI, SM, ME, BL, RRD, JDR, YC, VC,
HR, HS, RB, CRC and JMN. All authors have read and agreed to the published version of the manuscript.
Funding
French National Research Agency (ANR), Ecole Nationale Supérieure des Mines de Saint-Etienne,
Lafarge Division Plaster, OCP group, Technology Agency of the Czech Republic (TA CR) (Grant Number:
TH79020003) and German Federal Ministry of Education and Research (Project Number: 033RU020A) support
for this project is offered under the coordination of the ERA-MIN3 action, which has received funding from the
European Union under the Horizon 2020 Program (European Commission Grant Agreement No. 101003575).
Besides, this work also received support by the Federal Ministry of Education, Science and Research (BMBWF)
through Austria's Agency for Education and Internationalization (OeAD) [Grant Number: Africa UniNet P006
and P058 as well as WTZ CZ 14/2022 and HR 09/2022].
 7
Revised
8 Manuscript - Clean Version Click here to view linked References
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1
13 Phosphogypsum circular economy considerations:
2
14 A critical review from more than 65 storage sites worldwide
15
3
4
16 Essaid Bilal1, Hajar Bellefqih1, Véronique Bourgier1, Hamid Mazouz2, Delia-Georgeta Dumitraş3,
5
17 Frédéric Bard1, Marie Laborde1,4, Jean Pierre Caspar5, Bernard Guilhot1, Luisa Iatan1,6, Moussa
6
18 Bounakhla7, Măruţa Aurora Iancu3, Ştefan Marincea3, Meriem Essakhraoui8, Binlin Li9, Reymar R.
19 Diwa10, Jennyvi D. Ramirez10, Yelizaveta Chernysh11,12, Viktoriia Chubur11,12, Hynek Roubík11, Horst
7
8
20 Schmidt13, Redouane Beniazza14, Carlos Ruiz Cánovas15, José Miguel Nieto15, Nils Haneklaus13,16*
9
21 1
10 École Nationale Supérieure des Mines de Saint Etienne, CNRS UMR EVS, 5600, F42023 Saint Etienne, France
22 2 OCP Group, Jorf Lasfar, El Jadida, Morocco
11
23 3 Institut Géologique de Roumanie, Bucharest, Romania
12
13
24 4Cepsa Exploracion Y Produccion Slu, Madrid, Spain
14 5
25 6Division Lafarge Plâtre, Avignon, France
15
26 7 Institute of Geodynamics "Sabba S. Stefanescu" of Romanian Academy, Bucharest, Romania
16 Nuclear Centre of Energies, Sciences and Nuclear Techniques (CNESTEN), B.P. 1382, R.P. 10001, Rabat,
27 Morocco
17
18
28 8 Department of Chemisty, Faculty of Science. University Chouaib, Doukka, Morocco
19
29 9 College of Economics and Management, Yunnan Agricultural University, Kunming, China
20
30
10
Department of Science and Technology – Philippine Nuclear Research Institute (DOST-PNRI), Commonwealth
21 Ave., Diliman, Quezon City 1101, Philippines
31 11 Department of Sustainable Technologies, Faculty of Tropical AgriSciences, Czech University of Life Sciences,
22
32 Prague, 165 00 Prague, Czech Republic
23
24
33 12 Sumy State University, Rymskogo-Korsakova st. 2, 40007, Sumy, Ukraine
25
34
13
Technische Universität Bergakademie Freiberg, Institute of Chemical Technology, Leipziger Straße 29,
26
35 Freiberg, Germany
27 14
HTMR-Lab, 43150, Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco
36 15 University of Huelva, Department of Earth Sciences & Research Center on Natural Resources, Health & the
28
37 Environment, 21071 Huelva, Spain
29
38 16 Universität für Weiterbildung Krems, Td Lab Sustainable Mineral Resources, Dr.-Karl-Dorrek-Straße 30, 3500
30
31
39 Krems an der Donau, Austria
32
40
33 *Correspondence: [email protected]
41
34
42 Abstract: Nearly 300 million t of phosphogypsum (PG) are produced every year as a
35
43 byproduct from phosphate fertilizer production worldwide. Approximately 58% of the PG
36
44
37 are stacked, 28% are discharged in coastal waters and only 14% are further processed. This
45
38
46 critical review provides an overview of the physical-chemical properties of PG produced
39
47 from sedimentary and magmatic phosphate ore worldwide using various analytical tools.
40
48 Results from more than 25 years of work on PG at École des Mines de Saint-Étienne are
41
49 presented and critically discussed. In total PG samples from 67 industrial storage sites around
50 the world and PG samples synthesized under different conditions in the laboratory have been
42
51 considered. The low radioactivity present in PG (particularly PG produced from sedimentary
43
52 phosphate rock) was identified as the main challenge to using PG as a raw material in
44
53
45 construction. Water-soluble and volatile chemical compounds were identified as the main
54
46
55 challenge to environmentally sound PG management. Although PG does (in most cases) not
47
56 pose an immediate threat to the environment the authors recommend processing all PG
48
57 instead of storing or disposing it, to eliminate potential long-term risks and utilize a relevant
49
58 secondary resource.
59
50
60 Keywords: Phosphogypsum; circular economy; radioactivity; cleaner production
61
51
62
63
64 1
65
 7
8
9
10
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52
13 1 Introduction
14
53
15 Circular economy considerations are gaining more and more momentum among practitioners
54
16 and scholars (Corona et al., 2019; Kirchherr et al., 2017) putting pressure on the extractive
55
17 industries to also move away from a linear economy model to a more circular one. The nature
56
18 of mining obviously makes this challenging and circular economy considerations in mining
19
57 usually focus on minimizing natural resource extraction and residual waste (Kinnunen and
20
58 Kaksonen, 2019; Upadhyay et al., 2021) with a strong focus on waste, byproducts or mine
21
59 tailings (Asr et al., 2019; Ojeda-Pereira and Campos-Medina, 2021).
22
60
23 Phosphogypsum (PG) is the primary byproduct generated during the production of
24
61 phosphoric acid, an intermediate product in phosphate fertilizer production, from calcium
25
62 phosphate (apatite) ore. PG also exists in very small amounts in nature where it is the result
26
63 of natural guano processes as they took for instance place in the Cioclovina Cave located in
27
64 the Şureanu Mountains in Romania (Onac et al., 2002). Nearly 300 million t PG are produced
28
65
29 per year (Bouargane et al., 2023; Qin et al., 2023) of which 58% are dry- or wet stacked
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30 (Fuleihan, 2012), 28% are discharged into coastal waters, and only 14% are reused
67
31 (Rutherford et al., 1994). It is also noteworthy that there are more than 3 billion t (estimates
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32 in the literature usually range from 3-8 billion t) additional PG stacks worldwide (Chernysh
33
69 et al., 2021; Hermann et al., 2018; IAEA, 2013; Pliaka and Gaidajis, 2022; Tayibi et al.,
34
70 2009).
35
71
36 Specifically, PG is generated at the stage of wet-phosphoric acid (WPA) manufacturing at
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37 which phosphate rock (pre-concentrated phosphate ore) is digested with sulfuric acid at
38
73 approximately 80 °C as shown in Eq. 1 and schematically in Fig. 1.
39
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40 [𝐶𝑎3 (𝑃𝑂4 )2 ]3 𝐶𝑎𝐹2 + 10𝐻2 𝑆𝑂4 + 20𝐻2 𝑂 = 6𝐻3 𝑃𝑂4 + 10(𝐶𝑎𝑆𝑂4 2𝐻2 𝑂) + 2𝐻𝐹 (1)
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45
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48
49
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50
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51 Fig. 1: Overview and mass balance of phosphoric acid and phosphogypsum production
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77 from phosphate rock with sulfuric acid.
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54 The WPA process with sulfuric acid makes it possible to obtain PG in the form of a dihydrate
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55 (CaSO4·2H2O) while other processes lead to the production of a hemi-hydrate
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56 (CaSO4·0.5H2O) or an anhydrite (CaSO4). The attack of one t phosphate rock is usually done
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57 with 0.6 t of concentrated sulfuric acid that generates approximately 0.4 t of phosphoric acid
58
82 and 1.2 t of PG (Chang and Mantell, 1990; Hakim, 1997; van Selst et al., 1997).
59
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60 The importance of calcium sulfate dihydrate (CaSO4·2H2O) in industrial and agricultural
84
61 fields as well as potential environmental risks associated with PG stacking (Tayibi et al.,
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64 2
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 7
8
9
10
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12
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13 2009) and PG disposal in coastal waters (Aoun et al., 2015; Belahbib et al., 2021; Ben Salem
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14 and Ayadi, 2017; Boudaya et al., 2019; El Zrelli et al., 2015; Jia et al., 2022) has increased
87
15 interest in considering PG no longer a waste, but a byproduct of WPA production that could
16
88 be utilized in construction to substitute natural gypsum (Aagli et al., 2005; Abu-Eishah et al.,
17
89 2000; Burnett et al., 1996; Cárdenas-Escudero et al., 2011; Elkanzi and Chalabi, 1991;
18
90 Haneklaus et al., 2022; Mulopo and Omoregbe, 2012).
19
91
20 In addition, phosphate ore can contain elevated concentrations of valuable trace elements in
21
92 the form of rare earths (Akfas et al., 2023; Cánovas et al., 2016; Chen and Graedel, 2015;
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93 Emsbo et al., 2015; Ramirez et al., 2022) and uranium (Haneklaus, 2021). During WPA
23
94 production with sulfuric acid uranium largely (>80%) transfers to the phosphoric acid
24
95 product while the rare earths largely (>80%) transfer to the PG matrix (Rutherford et al.,
25
96 1994). Circular economy considerations in phosphate rock processing (Scholz and Wellmer,
26
97
27 2018), increased demand for uranium (Gabriel et al., 2013; Mudd, 2014) and rare earths
98
28 (Balaram, 2019; Liu and Chen, 2021), as well as geopolitical supply risks (Habib and
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29 Wenzel, 2014; Jyothi et al., 2020; Mancheri et al., 2019) have spurred research investigating
100
30 potential rare earths recovery from PG (Cánovas et al., 2019; Kandil et al., 2010; Lütke et
31
101 al., 2022; Rychkov et al., 2018; Walawalkar et al., 2016) and techno-economic feasibility of
32
102 uranium recovery from WPA (Beltrami et al., 2014; López et al., 2019; Shang et al., 2021;
33
103 Tulsidas et al., 2019; Ye et al., 2019). Industrial processes for uranium recovery from WPA
34
104 are available and were used in the United States in the 1980s until decreasing uranium prices
35
105
36 made the practice unprofitable in the 1990s (Haneklaus et al., 2017b, 2017a; Kim et al., 2016;
106
37 Steiner et al., 2020). It is noteworthy that direct leaching approaches for rare earths and
107
38 uranium recovery from phosphate ore are also under investigation (Al Khaledi et al., 2019;
108
39 Banihashemi et al., 2021; Guzmán et al., 1995; Roshdy et al., 2023) and uranium
40
109 concentrations in phosphate ore can reach concentrations exceeding those of commercial
41
110 uranium mines (Mwalongo et al., 2022). If successful, direct leaching approaches could limit
42
111 the radioactivity of PG considerably and thus make the material available as a secondary raw
43
112 material in construction.
44
45
113 Despite the interest in rare earth element (REE) recovery, PG still largely (about 96 wt%)
46
114 consists of gypsum. Depending on the type of the phosphate ore, traces of Cd, Zn, Pb, Hg,
47
115 Zr, Cu, Ba, REEs, Y, Th, U and 226Ra (which gives off 222Ra) are the most common and
48
116 relevant trace elements in PG. The radioactivity of the PG is usually 3-4 times higher than
49
117 that of the phosphate ore (Arhouni et al., 2022; Diwa et al., 2021; El-Bahi et al., 2017; Hakkar
50
118
51 et al., 2021; Qamouche et al., 2020). In Table 1 the radioactivity of PG is compared to
119
52 concrete, ceramic bricks and natural gypsum. While the values for 40K are smaller in the case
120
53 of PG, the radioactivity for 266Ra and 232Th can be 10 to 100 times higher than those of the
121
54 conventional building materials.
55
122
56 Table 1. Radioactivity of PG compared with the radioactivity of some building materials.
57 Th αBq/kg
232
Index I=
Products 266
Ra αBq/kg Radon gas 40
K γBq/kg
58 Thoron gas Ra/300+Th/200+K/3000
59 Concrete 25-50 20-50 200-1000 < 0,3
60 Bricks 50 15 600-1000 < 0,3
Natural gypsum 10-20 2-20 10-80 < 0,2
61 PG 100-2000 15-200 15-80 >1
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123
13 During WPA production, PG usually settles in a slurry and the resulting acidic process waters
124
14 are recycled. The recycling of the process waters further concentrates the trace elements in
125
15 the PG and the material is acidic because of the acids involved in the WPA production
16
126 process. In addition, fluorine from the phosphate ore is also present.
17
127
18 During dry stacking of PG rainwater and remaining process waters can combine to form a
128
19 hydraulic head that forces the infiltration of the acidic stack water into underlying aquifer
129
20 systems or surrounding water bodies (Al-Hwaiti et al., 2010; Bituh et al., 2013; Borilo et al.,
21
130 2012; El Zrelli et al., 2019; Lysandrou and Pashalidis, 2008; Pérez-lópez et al., 2016; Pérez-
22
131 López et al., 2015; Zhou et al., 2023). Besides, fine dust from the powder-like PG stacks can
23
132 be emitted causing respiratory problems (Adeoye et al., 2021; Lütke et al., 2020; Silva et al.,
24
133 2022). As a result, these wastes may be harmful to the environment and, in the long term,
25
134 induce health problems to local populations.
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27
135 PG represents both an environmental problem and an opportunity for valuable secondary
28
136 resource recovery. Within the context of present-day regulations and circular economy
29
137 considerations, the only reasonable way to dealing with this material is the development of
30
138 sustainable practices for complete (zero-waste) utilization of PG.
31
32
139 Given the large amounts of PG tailings produced annually it is not surprising that a number
33
140 of researchers have already investigated and reviewed potential zero-waste strategies for PG
34
141 utilization (Bouargane et al., 2023; Cánovas et al., 2018; Y. Cao et al., 2021; Chernysh et al.,
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142 2021; El-Didamony et al., 2013; Fornés et al., 2021; IFA, 2020; Kulczycka et al., 2016;
36
143
37 Mohammed et al., 2018; Qin et al., 2023; Rashad, 2017; Rosales et al., 2020; Saadaoui et al.,
144
38 2017).
39
145 Although present in relatively small quantities by weight and volume the trace-elements
40
146 (particularly the radioactive ones) associated with PG are usually the limiting factor to zero-
41
147
42 waste PG utilization. The quantities of these trace-elements in the PG depends largely on the
148
43 phosphate ores processed and the chemical processes (usually it is the WPA process with
149
44 sulfuric acid) used for phosphoric acid production (Macías et al., 2017; Rutherford et al.,
150
45 1995). A detailed knowledge of the trace-elements present in different PG stacks is thus of
46
151 profound interest when developing zero-waste PG utilization strategies that should be
47
152 applicable to a wide range of locations worldwide.
48
153
49 This critical review provides an overview of the physical-chemical properties of PG produced
154
50 from sedimentary and magmatic phosphate ore worldwide. Results from more than 25 years
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51 of work on PG at École des Mines de Saint-Étienne (EMSE) are for the first time presented
156
52 together and critically discussed. In total PG samples from 67 industrial sites around the
157
53 world and PG samples synthesized under different conditions in the laboratory have been
158
54 considered. The large sample set allowed the authors to draw new conclusions with regards
159
55 to PG texture and morphology (Chapter 3.1), PG chemistry (Chapter 3.2), PG dehydration
160
56 (Chapter 3.3) and PG synthesis (Chapter 3.4) that led to an improved discussion on PG
161
57 circular economy considerations (Chapter 4).
58
162
59 2 Materials and methods
60
163 PG samples (67 in total) and phosphate rock samples for production of PG in the laboratory
61
164 were provided by different phosphoric acid and phosphate fertilizer producing companies
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13 from around the world who anonymity was promised in exchange for samples. The samples
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14 were usually dried at low temperature to reduce the humidity and then analysed shortly after
167
15 they were received. For this review we largely relied on the historic data and only analysed
168
16 samples again if we felt data was incomplete or inconclusive. When PG samples are stored
169
17 the samples humidity content can change. The storage, even over longer periods of time,
170
18 should not affect the concentration of major elements and minor trace elements. Gamma ray
171
19 spectroscopy was used for radioactivity measurements and inductively coupled plasma mass
172
20 spectrometry (ICP-MS) was used to determine the concentration of trace elements in the PG.
173
21 In addition, PG samples were analyzed using inductively coupled plasma optical emission
174
22 spectroscopy (ICP-OES), infrared (IR) spectroscopy, scanning electron microscope (SEM),
175
23 thermogravimetric analysis (TGA) and X-ray diffraction (XRD).
24
176 3 Results and discussion
25
26
177 3.1 PG texture and morphology
27
178
28 The texture of PG depends on the production process, the particle size distribution of the
179
29 phosphate rock (relative speed of H+, SO42- and Ca2+ ionization), the concentration of the
30
180 phosphoric acid in the reactor slurry (the higher reaction speed, the higher the ion mobility)
31
181 and the solid/liquid ratio. Hemihydrate processes operate with 3-5% lower solids content if
32
182 compared with dihydrate processes. According to (Bilal and Caspar, 2004) five
33
183 morphological groups can be differentiated and examples of these different groups are
34
184
35 provided in Fig. 2.
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59 Fig. 2: PG types differentiated by their morphology and texture as rhombic type (Group 1),
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60 aggregate small rhombic type (Group 2), cluster type (Group 3), aggregate short needle
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61 type (Group 4) and needle type (Group 5).
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13 Group 1 is characterized by needle-shaped crystals with a uniform distribution of fine needles
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14 and elongated platelets with sizes varying from 10 to 120 µm and crystallites typically
191
15 ranging from 400-550 nm. The predominant phases in this group are gypsum, bassanite and
16
192 traces of anhydrite. The needles tend to form monoclinic gypsum crystals. The particle size
17
193 distribution of the phosphate rock feed in this group is usually as following: 160 µm (20-
18
194 30%), 125 µm (30-40%), 80 µm (40-60%).
19
195
20 Group 2 is characterized by a texture of fine agglomerated needles that are 5 to 30 µm in size
21
196 and crystallites ranging from 70-300 nm. Group 2 shows some of the characteristics of natural
22
197 gypsum but the material is only agglomerated so that the cohesive forces, bonding the grains
23
198 together is weaker. The concentration of the phosphoric acid in the reactor slurry in this group
24
199 is usually as following: 30% P2O5 in phosphoric acid with 58.6% water. Further increasing
25
200 the P2O5 content to 40% P2O5 and 44.7% water or even 52% P2O5 and 28.2% water will lead
26
201
27 to smaller and more irregular crystallization of the PG.
28
202 PG of group 3 can be described as polycrystalline aggregates that are in a disorderly manner.
29
203 The crystals tend to form bunches that are sometimes referred to as "pink sand". The solid
30
204 content in the slurry (solid/liquid ratio) is usually 30 vol%, if thick rhombic crystals are
31
205
32 present or 22 vol% if needle type crystallization is given. The rhombic crystals are preferred
206
33 for better filtration. In this context it is noteworthy that hemihydrate systems typically operate
207
34 with 3-5% lower solids content than dihydrate systems.
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208 The PG of group 4 differs significantly from the other groups. Here small grains are found
36
209
37 that typically have a roundish, pebble like shape. In direct contrast, the PG of group 5 consists
210
38 of very thin needle like crystals.
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211 The texture of the PG is particularly important for its potential use as a building material. For
40
212 example, in the plaster industry only certain gypsum crystal sizes are acceptable to produce
41
213
42 plasterboards. Group 1, 2 and 5 are acceptable. On the other hand, group 3 and 4 cannot be
214
43 used for plasterboard production but could be utilized in the cement industry or in agriculture.
215
44 The texture and morphology also influence further processing of the PG in processes such as
216
45 calcination.
46
217
47 3.2 PG CHEMISTRY
48
218 Phosphate rock is a mineral resource that contains phosphorus and is used as the raw material
49
219 for the production of phosphoric acid, which is a key ingredient in fertilizer. It is mainly
50
220
51 found in marine sedimentary deposits, igneous rocks, and guano. Approximately 75% of the
221
52 global phosphate resources come from sedimentary phosphate rocks, while 20-25% are
222
53 obtained from igneous deposits (Manning, 2008; Ptáček, 2016; Pufahl and Groat, 2017).
223
54 Guano, despite its high phosphate content, cannot be used on a global scale as it is not
55
224 available in enough quantities (Pufahl and Groat, 2017).
56
225
57 Practically, phosphoric acid can be produced from phosphate ore through two main routes:
226
58 the wet process, which involves the use of strong mineral acids for decomposing of the
227
59 phosphate, and the dry process, where the ore is heated in an electric furnace to produce
60
228 elemental phosphorus as an intermediary (Abouzeid, 2008; Da Silva and Kulay, 2005). The
61
229 wet process, in which phosphate rock is usually treated with sulfuric acid, is the prevalent
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13 way of manufacturing phosphoric acid today (Becker and others, 1989). This procedure leads
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14 to the production of considerable amounts of hydrated calcium sulfate, commonly referred
232
15 to as PG (see simplified mass balance in Fig. 1). In accordance with the temperature as well
16
233 as the phosphate and sulphate content of the solution, either calcium sulfate dihydrate (DH),
17
234 hemihydrate (HH) or anhydrite (AH) is formed.
18
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19 There are in fact two main wet processes that can be differentiated: single-stage processes
236
20 and recrystallization processes. Single-stage processes consist of only one reaction-
21
237 recrystallization step, regardless of the form of the obtained gypsum. The dihydrate (DH) and
22
238 hemihydrate (HH) processes are the two most prevalent methods in single-stage procedures.
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239 The dihydrate (DH) process is widely used due to its simplicity and flexibility in the treatment
24
240 of different types of phosphate rock and is therefore considered a reliable technique for
25
241 phosphoric acid production on industrial scale (Abdelouahhab et al., 2022; Abu-Eishah and
26
242
27 Abu-Jabal, 2001; Houghtaling, 1973). In this process, calcium sulfate in the form of gypsum
243
28 (dihydrate: CaSO4-2H2O) is obtained at a temperature between 70 and 80 °C and moderate
244
29 acid concentration. The energy efficiency of the DH process is lower due to the requirement
245
30 to finely ground feed rock and the resulting dilute phosphoric acid, which requires additional
31
246 energy for a subsequent concentration step. Phosphoric acid generated through the dihydrate
32
247 process is generally denoted as wet phosphoric acid (WPA). The Hemihydrate process (HH)
33
248 involves treating phosphate rocks at slightly higher temperatures (90-110°C) (De Vreugd et
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249 al., 1994; Gioia et al., 1977; Jansen et al., 1984). The PG obtained by this method is
35
250
36 contaminated with heavy metals and radioactive elements. The HH technique has the
251
37 advantage of requiring less grinding, but, the recovery rate of P 2O5 is slightly lower (Abu-
252
38 Eishah and Abu-Jabal, 2001).
39
253 Recrystallisation processes are intended to enhance the efficiency of recovering P 2O5,
40
254
41 including the production of a purer final filter cake and, in some cases, generating a higher-
255
42 strength acid directly. These processes include hemihydrate-dihydrate (HDH), hemihydrate
256
43 dihydrate recrystallization (HRC), and dihemihydrate (DH/HH) routes (Gobbitt, 2012;
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44 Koopman and Witkamp, 2000; Wang et al., 2021a, 2021b). In the HDH process, hemihydrate
45
258 (HH) is produced first and then filtered from the strong pure phosphoric acid product.
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259 Subsequently, the HH is transformed into dihydrate (DH) through recrystallization, leading
47
260 to higher process efficiencies. The primary disadvantages of the HDH technique are the
48
261 corrosion caused by the higher temperatures in the reactors and the intricate nature of the
49
262 process, that places a strain on the operating staff. The HRC starts with the decomposition of
50
263
51 the phosphate rock under the same conditions as the hemihydrate process, but without
264
52 filtration. Then, the product undergoes recrystallization to form dihydrate and is finally
265
53 filtered to obtain the final product. This results in an acid with a slightly higher strength
266
54 compared to that produced by the dihydrate processes. Furthermore, this technique leads to
55
267 the formation of a pure dihydrate byproduct. The DH/HH process forms dihydrate (DH),
56
268 which is filtered from phosphoric acid and then recrystallized to produce a pure hemihydrate
57
269 (HH) product. The HH product can be used directly in the production of plasterboards. Over
58
270 the last 20 years, the primary focus in WPA production has been the reduction of the energy
59
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60 costs. Despite low energy consumption per kilogram of P 2O5 produced, the total cost is
272
61 substantial due to high production rates. The most energy-intensive step in the production of
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13 phosphoric acid, if the chemical and not the thermal route is chosen, is associated with the
274
14 grinding of the phosphate rock. In fact, the processes that can handle coarser rock feeds (e.g.,
275
15 HH and HDH) have become more significant due to their overall lower energy consumption.
16
276 Table 2 shows the average composition of PG from different industrial production processes.
17
277 It is noteworthy that the individual production process influences the PG texture and
18
278 morphology that was discussed in the previous chapter. It is, however, not possible to link
19
279 the specific texture and morphology groups that were defined earlier (Group 1-5) directly to
20
280 the specific WPA processes listed in table 2.
21
22
281
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13 Table 2. Average PG composition from industrial production.
14 Phosphate Rock Sedimentary Magmatic Mixed
15 Process HDH Hitashi HDH Hydro Agry DH Jacob DH Prayon (S) DH Prayon (M) HRC Kemira
Loss of ignition (1000 °C) 17.78% 20.65% 20.68% 21.10% 19.71% 20.72%
16 Combined moisture 12.74% 22.91% 16.31% NR NR NR
17 Purity (sample dried at 250 °C) 93.27% 94.87% 91.83% NR 95.56% NR
18 pH (5% solution in distilled
3.9 4.4 3.3 NR NR NR
water)
19 Major elements
20 CaO% 30.53% 33.65% 33.73% 35.20% 35.85% 36.42%
SO3% 44.83% 45.82% 42.50% 44.47% 43.49% NR
21 SiO2% 4.70% 6.82% 4.38% 5.13% 2.39% 3.25%
22 Al2O3% 0.08% 0.14% 0.36% 0.19% 0.36% ND
Fe2O3% 0.18% 0.06% 0.12% 0.18% 0.25% 0.03%
23 P2O5% 1.31% 0.28% 0.78% 0.52% 0.70% 0.38%
24 Soluble P2O5 0.23% NR NR 0.37% 0.08% 0.02%
25 Na2O% 0.06% 0.06% 0.08% 0.04% 0.07% 0.02%
K2O% 0.03% 0.02% 0.10% 0.01% 0.05% 0.02%
26 TiO2% 0.03% 0.02% 0.03% 0.03% 0.29% ND
27 MgO% 0.04% 0.07% 0.02% <0.01% 0.04% ND
MnO% 0.01% 0.01% NR <0.01% 0.01% ND
28 F% 0.55% 0.61% 0.64% 0.45% 0.55% 0.05%
29 Soluble F 0.21% 0.35% 0.11% 0.31% 0.24% 0.11%
30 CO2% 0.21% 0.56% 0.39% 0.35% 0.28% 0.12%
Organic C 0.01% 0.11% 0.05% 0.04% 0.02% 0.01%
31 Chloride as Cl 1.78 mg/L 1.86 mg/L 0.88 mg/L 2.4 mg/L NR NR
32 Nitrate 8.70 mg/L 6.83 mg/L 6.86 mg/L 10.02 mg/L NR NR
Trace elements
33 As NR NR NR 2 ppm NR NR
34 Co 1 ppm 1 ppm 1 ppm <1 ppm 5 ppm 1 ppm
35 Zn 49 ppm 48 ppm 34 ppm 44 ppm 14 ppm 8 ppm
Pb 6 ppm 2 ppm 2 ppm 4 ppm <1 ppm ND
36 Cd 1 ppm 2 ppm 2 ppm 3 ppm <1 ppm ND
37 Ni 3 ppm 2 ppm 1 ppm 4 ppm 1 ppm ND
V 4 ppm 2 ppm 4 ppm 2 ppm 7 ppm 1 ppm
38 Cr 4 ppm 5 ppm 7 ppm 14 ppm 4 ppm 3 ppm
39 Cu 9 ppm 60 ppm 1 ppm 33 ppm 5 ppm 10 ppm
40 Ba 76 ppm 109 ppm 150 ppm 53 ppm 207 ppm 39 ppm
Sr 569 ppm 801 ppm 402 ppm NR 7,692 ppm 2,099 ppm
41 Th 1 ppm 1 ppm 1 ppm 3 ppm 42 ppm 4 ppm
42 U 2 ppm 5 ppm 3 ppm <1 ppm 52 ppm 8 ppm
Rare earths (including Y)
43 Y 18 ppm 27 ppm 72 ppm 140 ppm 133 ppm 27 ppm
44 La 9 ppm 14 ppm 39 ppm 49 ppm 1,215 ppm 165 ppm
45 Ce 10 ppm 15 ppm 20 ppm 31 ppm 1,998 ppm 246 ppm
Nd 7 ppm 11 ppm 25 ppm 37 ppm 921 ppm NR
46 Sm 1 ppm 2 ppm 6 ppm NR NR NR
47 Eu < 1 ppm 1 ppm 1 ppm 2 ppm NR NR
Gd 1 ppm 2 ppm 7 ppm 10 ppm NR NR
48 Tb < 1 ppm <1 ppm 1 ppm 3 ppm NR NR
49 Dy 1 ppm 2 ppm 7 ppm NR NR NR
50 Ho < 1 ppm <1 ppm 2 ppm 2 ppm NR NR
Er 1 ppm 1 ppm 5 ppm 6 ppm NR NR
51 Tm < 1 ppm <1 ppm 1 ppm NR NR NR
52 Yb 1 ppm 1 ppm 4 ppm 8 ppm NR NR
Lu < 1 ppm <1 ppm 1 ppm 1 ppm NR NR
53 ∑ REEs + Y 49 ppm 78 ppm 180 ppm 289 ppm 3,960 ppm 438 ppm
54 Radioactivity
55 226

232
Ra 211 Bq/kg 596 Bq/kg 414 Bq/kg 562 Bq/kg 267 Bq/kg NR
Th 5 Bq/kg <7 Bq/kg 5 Bq/kg 32 Bq/kg 185 Bq/kg NR
56 235
U <7 Bq/kg <16 Bq/kg 73 Bq/kg <9 Bq/kg 261 Bq/kg NR
57 40
K < 10 Bq/kg <26 Bq/kg 60 Bq/kg <12 Bq/kg NR NR
Radioacativity Index I 0.73 1.99 1.71 2.03 NR NR
58
283 NR: Not reported; ND = not detected
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29
285
30 Fig. 3: Distribution of PG (Magmatic PG and Sedimentary PG) in sum of REE versus Sr
31
286 diagram.
32
287
33 Generally, the PG samples produced from sedimentary phosphate rock (s-PG) have higher
288
34 SiO2 contents than the PG samples produced from magmatic phosphate rock (m-PG) with
289
35 the exception of Kola Peninsula PG samples that also have a high concentration of Na2O
36
290 (rock phosphate initials formed nepheline (Na3KAl4Si4O16)). The Y, Zr, Cu and Ba contents
37
291 are much higher in m-PG resulting from treatment of igneous apatite than in those from the
38
292 sulfuric treatment of sedimentary ores. Tunisian PG (an s-PG), for example, has relatively
39
293 high levels of Cd, Hg and Zn (Abbes et al., 2019; Choura, 2007; El Zrelli et al., 2015;
40
294 Rutherford et al., 1994). Approximately 80% of the Cd content passes preferably to the
41
295
42 phosphoric acid (Rutherford et al., 1994). If clean sulfuric acid is used, the major components
296
43 of the PG composition varies with the treatment of the phosphate rock while the trace
297
44 elements mainly depend on the origin of the ore. Macías et al. (2017) describe well how
298
45 sulfuric acid from pyrite roasting was used in the production of Huelva PG. This sulfuric acid
46
299 actually added a number of trace elements to the PG that did not result from the phosphate
47
300 rock itself. Radioactive elements, most notably 226Ra, 232Th, 40K result in the typical
48
301 radioactivity indexes (I = (Ra/300) + (Th/200) + (K/3000)) of 1.33 to 2.59 for s-PG and the
49
302 mixed PG (m-PG and s-PG). m-PG (particularly m-PG from Russia and some PG from
50
303
51 China) typically shows relatively low radioactivity indexes of 0.24 to 0.45. m-PG and also
304
52 mixed PG thus tend to show radioactivity indexes (I < 1) that theoretically allow for the use
305
53 of the material in construction as established by the International Commission on
306
54 Radiological Protection (ICRP) (Calderón-Morales et al., 2021; Campos et al., 2017;
55
307 Kuzmanović et al., 2021). In practice, the material is often not used since it is harder to sell
56
308 than a natural raw material that might show lower radioactivity, better strengths when
57
309 processed and pose much lower legal risks to producing companies that might have to adjust
58
310 to changing national regulations. Nevertheless, developments in PG treatment have been
59
311 made to further decrease the levels of radioactivity and impurities. The treatment methods
60
312
61 vary and may include washing, filtration, calcination, neutralization, leaching, and
313
62 purification, among others, to remove impurities and further reduce the radioactivity levels.
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314
13 The specific process used depends on the composition of the PG and the required end use.
315
14 The challenge of resolving the crystallization of thorium nesosilicate (ThSiO4), which is a
316
15 highly radioactive substance, in m-PG remains unresolved though. The radioactivity
16
317 measurements on different sites have shown that fine particles are richer in radon than
17
318 fractions above 30 μm. Some PGs that were previously washed, showed a decrease in levels
18
319 of heavy metals, Th, REEs, P2O5, Na2O and K2O.
19
20
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22
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32
33
34
320
35
321
36 Fig. 4: Distribution of PG (s-PG and m-PG) in Chondrite normalized diagram.
37
322
38 The contents of major impurities in PG vary according to the process type used, while the
323
39 trace concentrations would depend directly on the nature of the initial phosphate rock
324
40 (Rutherford et al., 1994). Only As, Ba, Cd, Cr, Pb, Hg, Se and Ag are classified as toxic
325
41 elements by the United States EPA (Environmental Protection Agency). Their content in PG
326
42 is usually less than the tolerated limit though. The fate of major and trace elements in gypsum
327
43 can be attributed to many processes such as precipitation in a fairly pure mineral phase,
328
44 inclusions of liquids, co-precipitation, formation of solid solutions and surface adsorption of
329
45 organic compounds or minerals. Free phosphoric acid, unreacted phosphates, sodium
330
46 hexafluorosilicate, sodium sulfate, fluorosilicic acid H2SiF6 and organic compounds adhere
331
47 to the surface of the gypsum crystals.
332
48 PG may contain heavy metals (Burnett et al., 1996; Hamdona et al., 1993) such as Pb, Cd,
333
49 Hg, Zn and Cu (Al-Masri et al., 2004; Cossa et al., 2001; Garrido et al., 2005; Van Der Sluis
334
50 et al., 1986) with Cu usually being the most abundant one (117 ppm). The Cd (usually 1 ppm)
335
51 of the Syrian PG is in 45 to 58 µm fine fractions while most heavy metals (Cr, Co, Zr, Cu,
336
52 Pb, Z n, Ag, Ni, Cd and V) are found in the particle size fraction less than 20 µm (Rutherford
337
53 et al., 1996; Silva et al., 2005).
338
54 REEs (except Ce), Th and Ba are essentially in a residual phase which corresponds to a small
339
55 fraction of rock phosphate or monazite: (Ce, La, Nd, Th)PO4 and has insoluble compounds
340
56 such as phosphates and silicates (Santos et al., 2006). 60 to 80% of the REEs (especially the
341
57 light ones: La to Sm) present in the phosphate rock are found in the PG. In both the dihydrate
342
58 or hemihydrate process the heavy REEs (Gd and Lu) migrate into the phosphoric acid. REEs,
343
59 Y, Ba and Sr are typically found in the fine fraction (<20 µm) (Silva et al., 2005).
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28
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345 Fig. 5: Radioactivity index of PG (s-PG, m-PG and mixed phosphate PG) versus Sr
30
346 diagram.
31
347
32 The m-PGs have higher strontium and rare earths contents (La and Ce mainly but also Pr,
348
33 Eu, Dy, Er and Lu) than s-PGs. In this work it was possible to draw a border zone, where the
34
349 Sr/Ca ratio is approximately 0.0057 (Sr/Ca <0.0057 = s-PG and Sr/Ca> 0.0057 = m-PG)
35
350 (Bilal et al., 2010).
36
351
37 Lanthanides retard the growth rate of gypsum crystals on all sides (preferably that with miller
352
38 indices (011) of needles for cerium) except for (-111) (Ce3 +> La3+> Eu3+> Er3+) because the
39
353 ionic radius of lanthanides such as cerium (128pm) is closer to that of calcium (126pm) than
40
354 lanthanides such as erbium (114pm)) (Koopman and Witkamp, 2002). In addition, Ce3+ and
41
355 Na+ form a solid solution with the hemihydrate during crystallization [(Na,Ce)(SO4)2.H2O +
42
356 CePO4.0,5H2O] – CaSO4.0,5H2O. This stabilizes the structure of the hemihydrate and slows
43
357
44 down the recrystallization of the dihydrate (Rutherford et al., 1994).
45
358 The other elements which can be substituted in the structure of the gypsum are Cd, Sr, Mg,
46
359 Na, K, Cl and Se. Cd2+ ions can replace Ca2+ ions because they have the same charge and
47
360 very similar ionic radii (1.12A and 1.07A respectively). The incorporation of Cd 2+ increases
48
361
49 with increasing H2SO4 (Rutherford et al., 1994).
50
362 The s-PGs usually have higher SiO2 contents than the m-PGs with the exception of the PG
51
363 produced from phosphate rock from the Kola Peninsula (Russia) (a m-PG that also has high
52
364 Na2O contents because they are made up of nepheline (Na3KAl4Si4O16)). Silica exists as
53
365
54 amorphous SiO2, quartz or SiO2-containing minerals (Elkanzi and Chalabi, 1991; Rutherford
366
55 et al., 1994). The selenium may be found in the form of CaSeO4.2H2O in the PG (Kruger and
367
56 Abriel, 1991). Fluorides precipitate in the form of complex crystalline salts, depending on
368
57 the concentrations of Al, Si, Mg, Na, Ca and sulphates dissolved in the acid. The most
58
369 common are calcium fluorosilicate and calcium fluoride. During the process of
59
370 manufacturing phosphoric acid, silicon increases the growth of the gypsum crystals along the
60
371 c axis and prevent the formation of aggregates because it tends to dissolve fluorine, which
61
372 does not syncrystallize in the PG. This therefore shows normal acicular growth.
62
63
64 13
65
 7
8
9
10
11
12
373
13 Aluminum and silica tend to form complexes with fluorides and therefore modify the
374
14 distribution of ionic species (6F- = SiF2-6 or AlF2-6). When the alkali concentration is low,
375
15 then chukhrovite: Ca4(SO4)(AlF6)SiF6).12H2O (whose structure has been described by
16
376 (Mathew et al., 1981) can precipitate. For high dissolved aluminum concentrations, fluorine
17
377 precipitates in the form of cryolite: (Na, K)3AlF6. The presence of magnesium changes the
18
378 fluorine precipitation mechanism. Specifically, the MgSiF6.6H2O phase appears. This group
19
379 of fluorosilicates crystallize in acicular form, which helps to improve the filterability of
20
380 calcium sulphate. When F, Mg, Na and Al are present, ralstonite: Na xMgxAl2-x (F, OH)6H2O
21
381
22 (x between 0.2 and 1.0 and the F/OH molar ratio between 3 and 1) is frequently formed (Lehr
382
23 et al., 1966). Fluorite and fluorapatite may be the solids controlling the solubility potentials
383
24 of fluorine in PG. The study of the PO4-SiO2-F system has shown an interdependence
384
25 between PO43- and F- because they are surely associated with the same phase, apatite
26
385 [Ca5(PO4, CO3)3(F, OH)2] which reprecipitates between F- and SiO2 because they would form
27
386 an alkaline hexa-Fluorosilicate (Na, K)2SiF6 (Burnett and Elzerman, 2001). The length/width
28
387 ratio (L/l) varies depending on the impurity present in the PG. Indeed, the presence of
29
388 fluorides (up to 2.09-2.80% in F-) or SiO2 (0.9-3.0%) leads to an increase of L/l while this
30
389
31 ratio remains unchanged with impurities such as CO2 (1.5-4.6%) and Fe2O3 (0.17- 0.48%) or
390
32 decreases slightly with Al2O3 (0.15-0.40%).
33
391 Dicalcium phosphate, monosodium sulfate and fluorophosphate can also enter the structure
34
392 of gypsum. A solid solution exists between the dicalcium phosphates because the HPO42-
35
393
36 ions replace the SO42- ions in the gypsum structure because these 2 ions have the same size,
394
37 molar mass and charge (Van Der Sluis et al., 1986). This substitution of phosphates in the
395
38 gypsum network during acidification is reduced with a high concentration of sulphates,
396
39 longer attack times of the phosphate rock, higher reaction temperatures and a large
40
397 percentage of solids. The incorporation of HPO42- decreases when H2SO4 increases. HPO42-
41
398 ions can be incorporated into the gypsum structure thus forming ardealite Ca(SO4)1-
42
399 x(HPO4)x.2H2O where x= 0.5 (Freyer and Voigt, 2003). One method to differentiate PG from
43
400 synthetic gypsum is for instance the analysis by IR spectroscopy. PG as an additional band
44
401 at 840 cm-1 relating to the absorption of the H2PO4 group (Hanna et al., 2009) that cannot be
45
402
46 observed in case of synthetic gypsum (Sebbahi et al., 1997).
47
403 El Moussaouiti et al. (1996) observed the appearance of a band at 836 cm-1 generated by
48
404 phosphate ions and the increase in intensity of that at 1094 cm-1 corresponds to the
49
405 superposition of the vibrations of SO42- and HPO42-. It was then proven (Guilhot et al., 1974)
50
406
51 that by IR spectroscopy, it is possible to highlight the syncrystallized HPO42- ions (836 and
407
52 1015 cm-1), HPO42- from the brushite phase (872 cm-1) and syncrystallized FPO32- (766 and
408
53 1025 cm-1). They can be measured (the heights of these bands depend on the content of
409
54 syncrystallized ions) (Guilhot et al., 1974). Gypsum crystals were observed to be needle-like
55
410 as long as the molar fraction of syncrystallized HPO42- ions does not exceed 0.07 to 0.085.
56
411 Beyond this value, the products appear in the form of lamellae groups in flower-like forms
57
412 (Guilhot et al., 1974). EDS analyzes (energy dispersive spectroscopy) do not show the
58
413 presence of phosphorus in PG (El Moussaouiti et al., 1996).
59
60
414 The complexes containing the AlF2-5 ions retard the growth of gypsum crystals because they
61
415 replace the SO42- ions and are mainly adsorbed on the faces (011) and (-111) hence a decrease
62
63
64 14
65
 7
8
9
10
11
12
416
13 in the L/l ratio of the crystals can be observed. The presence of aluminum fluorides causes
417
14 also the formation of small agglomerated crystals, having a hexagonal structure (Koopman
418
15 and Witkamp, 2002; Martynowicz, 1994; Martynowicz et al., 1996a, 1996b). From the Al
16
419 content of the phosphate rock and the values of the aluminum distribution coefficients, it is
17
420 possible to know the aluminum concentration during the hemihydrate process and the
18
421 probability that difficult to filter dihydrate crystals are formed. The applicability of different
19
422 phosphate rocks, in terms of their Al content, can be determined (Martynowicz et al., 1996b).
20
423 The hemihydrate obtained by calcining gypsum containing this co-crystallized species has a
21
424
22 setting-time which is less easy to control by adding a setting retarder than the pure
425
23 hemihydrate (Kitchen, 2007). During the phosphoric acid manufacturing process, the
426
24 presence of aluminum limits the growth of gypsum along the c-axis and promotes the
427
25 formation of aggregates. The presence of carbonates can lead to the formation of
26
428 rapidcreekite (Ca2(SO4)(CO3)4H2O) (Dydo et al., 2003).
27
429
28 3.3 PG DEHYDRATION
29
430 Efforts should focus on impurities, which play an important role in the hydration of PG to
30
431 use as substitutes for natural gypsum. Indeed, the s-PG shows conductometric curves highly
31
432
32 variable and late stabilization of conductivity (2.9 mS/cm) after 16 minutes and up to 32
433
33 minutes. Some of the s-PGs are characterized by a late conductivity stabilization, greater than
434
34 40 minutes and the conductivity at a high value of 4.1mS/cm. Some of S-PGs can further be
435
35 characterized by a late conductivity stabilization, greater than 40 minutes and the
36
436 conductivity at a high value of 4.1mS/cm.
37
437
38 The S-PG has impurities that slowly release and can result in an increase of the setting time
438
39 (Fig. 6). The conductivity stabilization time (setting time) reduced after many washings of s-
439
40 PG prior to dehydration. Experimental work in the EMSE laboratory (Bard and Bilal, 2011;
41
440 Bilal et al., 2014; Bourgier, 2007; Laborde, 2002) showed that the hydration depends mainly
42
441 on the presence of P2O5 in the PG, which was also confirmed more recently by others (see
43
442 for instance (Jia et al., 2021; Liu et al., 2020)). This effect disappeared when heating the PG
44
443 at 160 °C during which a reversal of the conductometric curves could be observed with
45
444
46 significant reduction of the setting time (Fig. 6). Excellent work on this was also carried out
445
47 by (Geraldo et al., 2020) for PG from Brazil as well as (Cao et al., 2022; W. Cao et al., 2021)
446
48 and (Li and Zhang, 2021) for PG from China. The relatively low required temperatures lead
447
49 to first experiments to consider waste heat (Mittal and Rakshit, 2020) or solar power (Palla
50
448 et al., 2022) for treatment of PG. Experimental laboratory studies have also shown that a
51
449 treatment consisting of washing with dilute citric acid solutions (Singh, 2002), oxalic acid
52
450 solutions (Cai et al., 2021) or sulfuric acid solutions (Bilal et al., 2014, 2010) helped reducing
53
451 soluble P2O5 in the PG considerably.
54
55
56
57
58
59
60
61
62
63
64 15
65
 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
452
36 Fig. 6: Conductometric curves of different PGs and stabilization time of conductivity
453
37 (setting time).
38
39
454 3.4 PG SYNTHESIS
40
41
455 To better understand the morphology, texture, and presence of impurities in PG various
42
456 syntheses of PG and gypsum were carried out. The first lesson learnt is that the composition
43
457 and morphology depend on the starting composition of the phosphate ore and the
44
458 concentrations of the sulfuric acid during the acid attack and the washing that follows. During
45
459 the acid attack little mobile elements are found in or with the PG such as P2O5 and F in solid
46
460
47 or dissolved form as: Ca (H2PO4).2H2O, Ca3PO4, CaF2, CaHPO4.2H2O (brushite),
461
48 CaFPO3.2H2O; and HPO42-, FPO32- ions and AlF52- (Kitchen, 2007; Martynowicz et al.,
462
49 1996a) co-crystallize in PG. During washing, several salts and acids are not completely
463
50 eliminated (H2PO4-, SiF6- or F-, Na+ and K+).
51
464
52 The excess of sulfuric acid and temperature in the acid attack plays an important role on the
465
53 texture and morphology of the PG that has already been discussed in Chapter 3.1 and is
466
54 further illustrated in Fig. 7. The excess sulfuric acid in the reactor slurry is the most effective
467
55 factor governing the quality of the crystallization. With very low sulfuric acid content, only
56
468 small diamond-like crystals are produced (Bard and Bilal, 2011). As the sulfate levels
57
469 increase, the crystal size increases and the shape of the crystals stretched out most of the time,
58
470 eventually becoming needle-like. The level of sulfuric acid is also responsible for the syn- or
59
471 co-crystallization of the P2O5.
60
61
62
63
64 16
65
 7
8
9
10
11
12
13 H2SO4 C = 15% C = 20% C = 30%
14 25°C
15
16
17
18 100µm
19
20 100µm
21
22 70°C
23
24
25 20µm
26
27
28
29 90°C
30
31 20µm
32
472
33
34
473 Fig. 7: Variation of the texture of the gypsum according to the content of H 2SO4 and the
35
474 temperature.
36
475
37 The crystal structure of brushite is similar to that of gypsum despite not being isostructural.
38
476 Both minerals belong to the monoclinic system, but they have different space groups (Cole
39
477 and Lancucki, 1974; Curry and Jones, 1971). This similarity makes the investigation of the
40
478 brushite-gypsum system by XRD challenging. In fact, the intense peaks that correspond to
41
479 the reflexion 020 (2θ = 11.7°) of brushite and gypsum are indistinguishable (Roode-Gutzmer
42
480 and Strydom, 1999). However, to differentiate these two phases the peaks at 2θ = 20.7° for
43
481
44 gypsum and 2θ = 21.0° for brushite should be considered. The two peaks are only discernible
482
45 for brushite contents greater than 1% in the gypsum and brushite mixture.
46
483 On the other hand, XRD analysis can reveal the presence of a new phase, ardealite
47
484 (Ca2(SO4)(HPO4).4H2O) when the phosphate ion content is above 7% (Fig. 8). For HPO42-
48
485
49 contents between 40% and 55%, the gypsum disappears and only the ardealite
486
50 (Ca2(SO4)(HPO4).4H2O) phase remains. For HPO42- contents between 55% and 95%,
487
51 ardealite coexists with brushite but beyond that only brushite is present. Rinaudo et al. (1994)
488
52 obtained the same order of appearance of the phases according to the variation of the contents
53
489 of HPO42- but they did not see the demixing of ardealite into ardealite and brushite after 55%
54
490 of the ion HPO42-.
55
491
56 In fact, the dehydration of brushite is less known than that of gypsum. Figure 9 highlights the
492
57 behaviour of brushite when it has been calcined at different temperatures. For temperatures
58
493 between 25 and 250˚C, only the brushite CaHPO4.2H2O and monetite CaHPO4 phases were
59
494 observed. At 250° C, the initial brushite transformed into monetite after losing its structural
60
495 water. The Ca3(PO4)2 and Ca(H2PO4).H2O phases were not detected by XRD. According to
61
496 Lang Dupont (1985), it is impossible to obtain pure anhydrous calcium phosphate since
62
63
64 17
65
 7
8
9
10
11
12
497
13 before total dehydration, calcium pyrophosphate Ca2P2O7 begins to form. There is always a
498
14 superposition of the two reactions. During the dehydration of the gypsum-brushite mixtures,
499
15 the transformation of anhydrite III into anhydrite II occurs at higher temperatures than for
16
500 pure gypsum. The brushite present in the mixture is transformed at 150 °C in two phases
17
501 (Fig. 10): 24% brushite and 76% monetite (semi-hydrated phase). This brushite differs from
18
502 the first by its physicochemical characteristics.
19
503
20
21
504 Ca (SO )(HPO ).4H O

Ca (SO )(HPO ).4H O

).4H O
22 2

2
4 4 2O 2

Ca2SO4)(HPOH4)4H2O
4)4H2O
23

CaHPO .2H O

CaHPO .2H O
505
.2H O

(SO )(HPO)4H
.2H O

CaHPO42H24O 2
CaHPO42H24O 2
4 2

24
4 2

4
42H2O

42H2O

506

2 4)(HPOH
25
2 )(HPOH
+

+
CaSO

CaSO

26
507
CaSO

CaSO

4
27
4

28
2SO
Ca2SO

508

2
CaCa

29
509
30
31
510
32

Brushite
Brushite
brushite

brushite
Ardealite
ardéalite

Ardealite
Ardealite

ardéalite
ardéalite
Gypsum
gypse

gypse

33
511
Gypsum

34 +
+

512
35
36
513 2- 2-
37 SO
SO4 2- HPO4 2-
HPO
38
514 4 4
39 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
515
40
41
516
42
517
43 Fig. 8: Order of appearance of the phases (XRD analyzes) as a function of the variation in
44
518 the HPO42- contents.
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64 18
65
 7
8
9
10
11
12
13
14
CaHPO4.2H2O
15
16 Ca2P2O7
17 CaHPO4
18
600 °C
19
20 450 °C
350 °C
400
21
Lin (Counts)

22 300 250 °C
23 200 °C
200 175 °C
24 150 °C
25 125 °C
100
100 °C
26
27 0 25 °C
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
28
519
29 2-Theta - Scale
Temp.: 25 °C (Room) X + 19.2 mm - Y + 42.0 mm - Temp.: 450 °C
30 X + 3.2 mm - Y + 7.0 mm - Temp.: 100 °C X + 22.4 mm - Y + 49.0 mm - Temp.: 600 °C
520 Fig. 9: A series of XRD patterns taken during
X + 4.8 mm - Y + 10.5 mm - Temp.: 125 °C the calcination of brushite
31 X + 6.4 mm - Y + 14.0 mm - Temp.: 150 °C
32
521 X + 8.0 mm - Y + 17.5 mm - Temp.: 175 °C
X + 9.6 mm - Y + 21.0 mm - Temp.: 200 °C
33 X + 12.8 mm - Y + 28.0 mm - Temp.: 250 °C
522
34 X + 16.0 mm - Y + 35.0 mm - Temp.: 350 °C

35
523
36
37
38
Bassanite + Monetite + Brushite
Bassanite + Brushite + Monetite

Brushite + Monetite + Bassanite

39
40
Brushite + Monetite +

41
42
(Bassanite)

43
Bassanite

44
45
46
47
48
49
50
51
52 CaSO4 CaHPO4
53
54
524 0 50 100
55
56
525 Fig. 10: Phases present in the CaSO4.2H2O - CaHPO4.2H2O system heated to 150 °C
57
526 determined by XRD.
58
59
527
60
528
61
62
63
64 19
65
 7
8
9
10
11
12
529
13 In situ XRD analysis revealed that ardealite (Ca(HPO4)(SO4).4H2O) was decomposed during
530
14 heat treatment into brushite (CaHPO4.2H2O), monetite (CaHPO4) and bassanite
531
15 (CaSO4.0,5H2O) (see Fig.11). At a temperature above 150 °C, the bassanite was transformed
16
532 into anhydrite III, while at 250 °C, brushite was entirely replaced by monetite. Subsequently,
17
533 between 250˚C and 350˚C, the appearance of stable anhydrite II CaSO4 and amorphous
18
534 calcium pyrophosphate Ca2P2O7 had been observed. This explanation of the dehydration of
19
535 ardealite is consistent with that of Balenzano et al. (1984) and Secco et al. (2015).
20
536
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
537
40
538
41 Fig. 11: A series of XRD patterns taken during the calcination of ardealite.
42
539 The infrared absorption spectra of the gypsum-brushite mixtures are shown in Fig. 12 and
43
540
44 the characters and intensities of the absorption bands obtained on the different gypsum and
541
45 brushite mixtures are given in Table 3. The band assignments are in agreement with the work
542
46 of (Dumitras et al., 2004) which was based on the work of (Berry and Baddiel, 1967; Murat
543
47 and Foucault, 1977; Petrov et al., 1967; Tortet et al., 1996; Trpkovska et al., 1999). Infrared
48
544 absorption spectra of the mixture containing 50% gypsum and 50% brushite (CaHPO4.2H2O)
49
545 show the characteristic bands of gypsum and brushite. They are very different from those of
50
546 ardealite (Ca2(SO4)(HPO4).4H2O). IR can thus be used as a relatively easy method to
51
547 distinguish the mechanical mixtures of gypsum-brushite of a phase of the ardealite type
52
548 containing in equal proportions HPO42- and SO42-.
53
54
549 Table 3: Summary of the waves corresponding to the absorption bands of HPO42- observed
55
550 on the infrared spectra of solid solution gypsum and of the gypsum-brushite mixture.
56
57 Characteristic bands of HPO42- wavelengths (cm-1)
58 2-
HPO4 (Brushite) 1650 986 872 524
59 HPO42- syn-crystallized 1017 836
60
551
61
62
63
64 20
65
 7
8
9
10
11
12
552
13
14
15
16
17 10%
18
19
20
40%
21
22
23 50%
24
25
26
27
28
29
30
31
32
33
553
34
35
554 Fig. 12: Infrared absorption spectrum of a solid solution as a function of the contents by
36
555
37 weight of CaHPO42H2O / CaSO42HO + CaHPO42H2O) = 5, 10, 12, 13, 15, 20, 30, 40 and
556
38 50.
39
557
40 Brushite in a gypsum-brushite mixture, is detectable in the infrared spectrum by the
558
41 absorption band 872 cm-1 (see Fig. 12) corresponding to the vibration of symmetrical valence
559
42 stretching P-O(H) of the structural HPO42- group. If the gypsum-brushite mixture is
43
560 homogeneous, it is possible to relate it to the height of this absorption band and the amount
44
561 of brushite introduced (Aslanian et al., 1980).
45
562
46 In a solid solution with 5wt% HPO42- only the band at 837 cm−1 is present (see Fig. 12),
563
47 representing the syncrystallized phosphate ion HPO42-, while the band at 872 cm−1 appears at
48
564 10wt% HPO42- in the solid solution corresponds to the demixing of the solid solution gypsum
49
565 (SO42-, HPO42-) into two gypsum phases (HPO42- syncrystallized) and ardealite Ca(SO4)1−
50
566 2- −1
x(HPO4)x2H2O. At 40-50 wt% HPO4 only the 872 cm band remains which corresponds to
51
567 the HPO42- ion of ardealite.
52
53
568 The IR studies of gypsum samples containing varying amounts of HPO 42- showed that the
54
569 primary absorption band of syncrystallized HPO42- ions, found at 836 cm-1, increased in
55
570 intensity until it reached a P/S ratio of approximately 0.1111 (see Fig. 13). However, as the
56
571 proportion of inserted phosphate ions continued to rise, the intensity of the absorption band
57
572 decreased and eventually disappeared when the P/S ratio reached 0.4287. Simultaneously,
58
573
59 the characteristic absorption band of ardealite appeared for P/S = 0.1111 at 864 cm-1. The
574
60 intensity of this band raised with an increase of the P2O5 percentage and gradually shifted to
575
61 higher wavelengths. For P/S ≅ 4, the absorption band was found at 870 cm-1, and it shifted
62
63
64 21
65
 7
8
9
10
11
12
576
13 to 872 cm-1 for pure brushite. Therefore, it was impossible for us to establish a limit between
577
14 the passage from the ardealite phase to the brushite phase using this analysis technique. In
578
15 this spectral range, Aslanian et al., (1980) had only identified two absorption bands: the band
16
579 at 850 cm-1 which appeared for a P/S = 0.080 but was not attributed, and the 872 cm-1 band
17
580 identified for a P/S ratio above 0.25. Similarly, Rinaudo and Abbona, (1988) also found that
18
581 the spectrum of synthetic ardealite is different from that of a mixture of gypsum and brushite.
19
582 However, they have not mentioned the presence of the 864 cm-1 absorption band. It would
20
583 be interesting to analyse in more detail the part where HPO42- > 96%. Contrary to the HPO42-
21
584
22 < 3% area, the characteristic absorption bands of HPO42- (SO42- ions substituted by HPO42-)
585
23 in the gypsum phase that can be observed relatively easily, it seems difficult to determine the
586
24 absorption bands relative to SO42- ions in the brushite lattice, considering the observations
587
25 made above. We were indeed not able to observe a new absorption band but only a shift of
26
588 the band located at 872 cm-1 relative to the brushite.
27
589
28 In the spectral range from 500 to 700 cm-1, it was observed that as the amount of P2O5
590
29 increased, the absorption band characteristic of syncrystallized HPO 42- ions located at
591
30 527 cm-1 intensified and shifted to 517 cm-1, a band attributed to pure brushite (see Fig. 13).
31
592 Moreover, for P/S=4, the bands at 668 and 597 cm-1 disappeared and a new absorption band
32
593 at 576 cm- 1 could be observed.
33
594
34 The solid solution containing HPO42- syncrystallized ions was characterized with respect to
595
35 the gypsum-brushite mechanical mixture by the presence of two absorption bands: 1017cm -
36
596 1
corresponding to the ν3 vibration of asymmetric valence stretching P-O(H) of the structural
37
597 group (PO4)3- and 837 cm-1 vibration linked to the structural group HPO42- the latter is on
38
598 average twice as important. It can be noted that there is a very good correlation between the
39
599 quantity of syncrystallized HPO42- ions introduced into the solid solution gypsum and the
40
600
41 height of the peak of the absorption band (Fig. 14). If the gypsum-brushite mixture is
601
42 homogeneous, it is possible to relate the height of this absorption band to the amount of
602
43 brushite introduced (see Fig. 14) (Aslanian et al., 1980; Bard and Bilal, 2011; Bilal et al.,
603
44 2014; Bourgier, 2007; Dumitras et al., 2011, 2004; Laborde, 2002; Marincea et al., 2004).
45
604
46
47
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48
49
606
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51
607
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33
34
608
35
36
609 Fig. 13: Infrared spectra of gypsum samples containing 0.00% < HPO42- <100.00% A and
37
610 B) 700-950 cm-1 C and D) 500-700 cm-1.
38
611 CaSO4.2H2O, P/S = 0.0526, 0.1111, 0.1364, 0.1494, 0.1522, 0.2500 (Figs. A and C)
39
612 CaSO4.2H2O, P/S = 0.1111, 0.2500, 0.4287, 0.6666, 1.0000, 1.5000, 4.0000, CaHPO4.2H2O (Figs. B and D)
40
613
41
42
614
43
Peak height 837cm (% transmittance)

44
45
3

46
47
48
2

49
-1

50
51
1

52
53
54
0

55 0 0.5 1 1.5 2 2.5 3

56 CaHPO42H2O / (CaSO42H2O + CaHPO42H2O)
57
615
58
59
616 Fig. 14: Correlation between the height of the 837 cm-1 absorption band and the content of
60
617 HPO42- syncrystallized ions.
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64 23
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618
13
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15 5

16 0
17
-5
18
19
Heatflow (mW)
-10 Ardealite
20 -15

21 -20
22
-25
23 Gypsum
-30
24
Brushite
25 -35
0 100 200 300 400 500 600
26 Temperature (°C)
27
619
28
620 Fig. 15: Dehydration of the pure gypsum (blue), brushite (red) and ardealite (green) phases.
29
30
621 During the dehydration of synthetic PG, the transformation of anhydrite III to anhydrite II
31
622 occurs at higher temperatures than for pure gypsum. The brushite present in the mixture is
32
623 transformed at 150 °C in two phases (Fig. 15): 24% brushite and 76% monetite (semi-
33
624 hydrated phase). On the DSC curve an endothermic effect can be observed at 156°C and
34
625
35 199°C corresponding to the departure of molecular water. The work on synthetic brushite by
626
36 (C. Rinaudo and Abbona, 1988; Sivakumar et al., 1998) agree with our observations on this
627
37 double endothermic effects.
38
628 The mass loss in the first step is 4.11% corresponding to weakly bound molecular water and
39
629
40 the second mass loss is 16.42%, or 20.53% of the total cumulative mass loss. The third mass
630
41 loss of 4.81% at 415 °C corresponds to the disappearance of monetite and the formation of
631
42 Ca2P2O7 corresponding to the exothermic peak on the DSC curve (Fig. 16).
43
632 The dehydration of ardealite occurs in several stages with endothermic peaks at 135 °C, 165
44
633
45 °C, 190 °C and 215 °C (C. Rinaudo and Abbona, 1988) and results in a total mass loss of
634
46 about 20%.
47
635
48
49
50
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52
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61
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64 24
65
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8
9
10
11
12
636
13
14
Solid solutions
15
16 9
17 8
18 Delay of hydration
7
19
Conductivity (mS/cm)

6 After cooking PG
20
5
21
22 4 1.50% Syn- or Co–crystallized P2O5
3
23
2 0.25%
24
1
25 Setting time
26 0
0 10 20 30 40 50 60
27 Tim e (min)
28
637
29
638
30 Fig. 16: Conductometric curves and stabilization time of conductivity (setting time) of
31
639 synthetic PG with different P2O5 contents and hydration of synthetic PG cooking.
32
33
640
34
35
641 4 PG circular economy considerations
36
642
37 The extractive nature of mining does not enable the raw material industry to become fully
643
38 circular. In other words, the nature of mining will unavoidably make it environmentally
644
39 disruptive (Schoenberger, 2016; Zhao et al., 2012). There is still plenty of room for the
40
645 mining industry (de la Torre de Palacios and Espí Rodríguez, 2022; Gorman and Dzombak,
41
646 2018; Laurence, 2011; Littleboy et al., 2019; Whitmore, 2006), and also the phosphate ore
42
647 mining industry (Geissler et al., 2018) to become more sustainable though. The extractive
43
648 industries surely are part of the economy, providing the raw materials for all other activities,
44
649
45 and they will therefore also be a part of any envisioned circular economy (Lèbre et al., 2017a;
650
46 Singh et al., 2020). Circular economy considerations in mining usually focus on minimizing
651
47 the environmental impact during raw material extraction (Input in Fig. 17) and minimizing
652
48 the quantity as well as the environmental impact of the produced waste (Output in Fig. 17)
49
653 (Cimprich et al., 2022; Gedam et al., 2021; Luthra et al., 2022; Tayebi-Khorami et al., 2019).
50
654 There is a fine, and we like to think permeable, line between what is a waste and what might
51
655 be a resource (Lèbre et al., 2017b). This is even more true for naturally occurring radioactive
52
656 material (NORM) or technologically enhanced NORM (TENORM) such as PG that are often
53
657 overlooked in circular economy considerations (Tsioka and Voudrias, 2020; Turcanu et al.,
54
658
55 2022). Figure 17 provides a simplified illustration of our understanding of the circular
659
56 economy with considerations for fresh- and stacked PG. Specifically, we believe that fresh
660
57 PG should ideally not be considered a waste but be processed and thus stay within the circular
661
58 economy consisting of production, consumption, and recycling in Fig. 17 (Xu et al., 2019).
59
662 The considerable quantities of stacked PG (3-8 billion t worldwide) can also be processed
60
663 and thus added to the circular economy, minimizing raw material extraction, for instance for
61
664 natural gypsum and rare earths, elsewhere.
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64 25
65
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22
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26
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31
665
32
33
666 Fig. 17: Circular economy considerations for PG.
34
667
35 Policies to support the re-use of PG as illustrated in Fig. 17 are already underway (Cui et al.,
668
36 2022) and we sincerely hope that this review will add knowledge that can further foster the
669
37 utilization of fresh and stacked PG as a valuable secondary resource. This practice would not
670
38 only reduce environmental risks associated with storing PG by free a considerable amount of
671
39 land that can then be used for other purposes.
40
672 This work allowed us to compare a relatively large number of PG samples with one another
41
673 and learn about the different national practices and regulations in the process. It is challenging
42
674 to draw generally applicable conclusions from such a large dataset. We are confident to share
43
675 though that directly marketable PG needs to fulfill strict specification that usually depend on
44
676 its free moisture content, total P2O5 content, soluble and insoluble P2O5 content, the PG
45
677 insoluble F and soluble F content, pH, the particle size, morphology, texture, and
46
678 radioactivity index. The chapters of this review were in fact designed accordingly to add our
47
679
48 experience about PG analysis and processing. This experience also showed that washing
680
49 with diluted sulfuric acid, morphological and chemical characterization can be simple but
681
50 powerful methods to identify marketable PG.
51
682 Table 4 provides an example of the PG specifications required for the plaster industry that
52
683 we consider to be one of the most important takers of fresh and stacked PG worldwide. In
53
684 this context, it is noteworthy that in case of fresh PG changes in the current phosphoric acid
54
685 production processes (sulfuric acid use, the temperature of the reaction, the particle size of
55
686 the phosphate rock and a mixture of different types of magmatic and sedimentary phosphate
56
687 rock to influence the morphology and texture of the PG) can have significant effects on the
57
688 resulting PG.
58
689
59 As of now the phosphate fertilizer industry designs the phosphoric acid production processes
690
60 with the aim of producing the best fertilizers (as they should). Not at all considering or having
691
61 to consider the quality of the produced PG, can however, result in PG that is a particularly
62
63
64 26
65
 7
8
9
10
11
12
692
13 hard sell. We sincerely hope that this one-product-thinking will change to a multi-product-
693
14 thinking as part of which the quality of both phosphoric acid and PG are considered in the
694
15 process designs, so that both can later be sold at ease.
16
695 Table 4: Specification of PG for use in the plaster industry.
17
18 Free Moisture % If possible <15
19 Total P2O5% <1
20 Insoluble P2O5% <0.6
21 Soluble P2O5% <0.05
22 Co-crystallized P2O5% < 0,5
23 Total F <1
24 Insoluble F% <0.6
25 Co-crystallized F < 0,15
26 Soluble F% <0.05
27 Na2O % < 0,5
28 MgO % < 0,6
29
Chloride < 0,01
30
pH 5< pH < 8
31
SiO2 (quartz & non soluble in HCl acid) < 1,25%
32
33 PARTICLE SIZE: d50 50 µm < d 50 < 100 µm
No needles, no spherical shapes
34
RadioactivityIndex I = Index for final product < 1
35
Ra/300+Th/200+K/3000
36
37 Additives None which can penalize setting times
38 Size specification for shipping Pellets 20/30mm or <70mm
39 Size specification for utilization Mixed with clinker then ground
696
40
697
41
42
698
43 5 Conclusions and outlook
44
699
45 This critical review summarized over 25 years of work on PG utilization at EMSE. PG
700
46 samples from more than 65 storage sides were considered and novel conclusions on s-PG
701
47 and m-PG, as well as how the processing parameters of these PGs define the PG composition
702
48 are provided. Besides, the critical review puts an emphasis on providing useful observation
703
49 for PG analysis and introduces an important way to group PG samples by its texture and
704
50 morphology that is particularly relevant if PG is investigated for potential use as a
705
51 construction material. Although a relatively large set of samples was used in this critical
706
52 review tracing the PG back to the raw material utilized was sometimes challenging as
707
53 industrial samples were used and the companies providing them had an interest to not fully
708
54 disclose processing as well as mixing parameters. Future studies should aim for more
709
55 transparency and also more consistency with regards to sample analysis and comparison so
710
56 that further conclusions, relevant for the utilization of PG can be drawn. Recycling of PG is
711
57 an extremely active topic and we provided novel, higher-level analysis of the role of fresh
712
58 and stacked PG in an envisioned circular economy.
59
713
60 Ethical Approval
61
714 Not applicable.
62
63
64 27
65
 7
8
9
10
11
12
715
13 Consent to Participate
14
716 Not applicable.
15
16
717 Consent to Publish
17
718
18 Not applicable.
19
719 Authors Statement
20
720
21 Conceptualization, Methodology, Writing-Reviewing and Editing: EB; Writing-Reviewing
22
721 and Editing: HB, NH; Reviewing and Editing: VB, HM, DGD, FB, ML, JPC, BG, LI, MB,
23
722 MAI, SM, ME, BL, RRD, JDR, YC, VC, HR, HS, RB, CRC and JMN. All authors have read
24
723 and agreed to the published version of the manuscript.
25
724
26 Funding
27
725
28 French National Research Agency (ANR), Ecole Nationale Supérieure des Mines de Saint-
726
29 Etienne, Lafarge Division Plaster, OCP group, Technology Agency of the Czech Republic
727
30 (TA CR) (Grant Number: TH79020003) and German Federal Ministry of Education and
728
31 Research (Project Number: 033RU020A) support for this project is offered under the
32
729 coordination of the ERA-MIN3 action, which has received funding from the European Union
33
730 under the Horizon 2020 Program (European Commission Grant Agreement No. 101003575).
34
731 Besides, this work also received support by the Federal Ministry of Education, Science and
35
732 Research (BMBWF) through Austria's Agency for Education and Internationalization
36
733 (OeAD) [Grant Number: Africa UniNet P006 and P058 as well as WTZ CZ 14/2022 and HR
37
734
38 09/2022].
39
735 Competing Interests
40
736
41 The authors have no relevant financial or non-financial interests to disclose.
42
737
43 Availability of Data and Materials
44
738 Data used is openly accessible or can be made available on request.
45
739
46 References
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840 impurities in waste phosphogypsum for the production of cement. Sci. Total Environ. 780,
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changes marked) Manuscript - Highlighted Version (with

1 Phosphogypsum circular economy considerations:

2 A critical review from more than 650 storage sitesamples collected worldwide
3
4 Essaid Bilal1, Hajar Bellefqih1, Véronique Bourgier1, Hamid Mazouz2, Delia-Georgeta Dumitraş3,
5 Frédéric Bard1, Marie Laborde1,4, Jean Pierre Caspar5, Bernard Guilhot1, Luisa Iatan1,6, Moussa
6 Bounakhla7, Măruţa Aurora Iancu3, Ştefan Marincea3, Meriem Essakhraoui8, Binlin Li9, Reymar R.
7 Diwa10, Jennyvi D. Ramirez10, Yelizaveta Chernysh11,12, Viktoriia Chubur11,12, Hynek Roubík11, Horst
8 Schmidt13, Redouane Beniazza14, Carlos Ruiz Cánovas15, José Miguel Nieto15, Nils Haneklaus13,16*
9
10 1
École Nationale Supérieure des Mines de Saint Etienne, CNRS UMR EVS, 5600, F42023 Saint Etienne, France
11 2
OCP Group, Jorf Lasfar, El Jadida, Morocco
12 3
Institut Géologique de Roumanie, Bucharest, Romania
13 4
Cepsa Exploracion Y Produccion Slu, Madrid, Spain
14 5
Division Lafarge Plâtre, Avignon, France
15 6
Institute of Geodynamics "Sabba S. Stefanescu" of Romanian Academy, Bucharest, Romania
16 7
Nuclear Centre of Energies, Sciences and Nuclear Techniques (CNESTEN), B.P. 1382, R.P. 10001, Rabat,
17 Morocco
18 8
Department of Chemisty, Faculty of Science. University Chouaib, Doukka, Morocco
19 9
College of Economics and Management, Yunnan Agricultural University, Kunming, China
20 10
Department of Science and Technology – Philippine Nuclear Research Institute (DOST-PNRI), Commonwealth
21 Ave., Diliman, Quezon City 1101, Philippines
22 11
Department of Sustainable Technologies, Faculty of Tropical AgriSciences, Czech University of Life Sciences,
23 Prague, 165 00 Prague, Czech Republic
24 12
Sumy State University, Rymskogo-Korsakova st. 2, 40007, Sumy, Ukraine
25 13
Technische Universität Bergakademie Freiberg, Institute of Chemical Technology, Leipziger Straße 29,
26 Freiberg, Germany
27 14
HTMR-Lab, 43150, Mohammed VI Polytechnic University (UM6P), Benguerir, Morocco
28 15
University of Huelva, Department of Earth Sciences & Research Center on Natural Resources, Health & the
29 Environment, 21071 Huelva, Spain
30 16
Universität für Weiterbildung Krems, Td Lab Sustainable Mineral Resources, Dr.-Karl-Dorrek-Straße 30, 3500
31 Krems an der Donau, Austria
32
33 *Correspondence: [email protected]@chemie.tu-freiberg.de
34
35 Abstract: Nearly 300 million t of phosphogypsum (PG) are produced every year as a
36 byproduct from phosphate fertilizer production worldwide. Approximately 58% of the PG
37 are stacked, 28% are discharged in coastal waters and only 14% are further processed. This
38 critical review provides an overview of the physical-chemical properties of PG produced
39 from sedimentary and magmatic phosphate ore worldwide. This critical review provides an
40 overview of the physical-chemical properties of PG produced from sedimentary and
41 magmatic phosphate ore worldwide using various analytical tools. Results from more than
42 25 years of work on PG at École des Mines de Saint-Étienne are presented and critically
43 discussed. In total PG samples from 67 industrial storage sites around the world and PG
44 samples synthesized under different conditions in the laboratory have been considered. The
45 low radioactivity present in PG (particularly PG produced from sedimentary phosphate rock)
46 was identified as the main challenge to using PG as a raw material in construction. Water-
47 soluble and volatile chemical compounds were identified as the main challenge to
48 environmentally sound PG management. Although PG does (in most cases) not pose an
49 immediate threat to the environment the authors recommend processing all PG instead of
50 storing or disposing it, to eliminate potential long-term risks and utilize a relevant secondary
51 resource.

1
52 Keywords: Phosphogypsum; circular economy; radioactivity; cleaner production
53

54 1 Introduction

55 Circular economy considerations are gaining more and more momentum among practitioners
56 and scholars (Corona et al., 2019; Kirchherr et al., 2017) putting pressure on the extractive
57 industries to also move away from a linear economy model to a more circular one. The nature
58 of mining obviously makes this challenging and circular economy considerations in mining
59 usually focus on minimizing natural resource extraction and residual waste (Kinnunen and
60 Kaksonen, 2019; Upadhyay et al., 2021)(Kinnunen and Kaksonen 2019; Tayebi-Khorami et Formatted: Hi
61 al. 2019; Upadhyay et al. 2021; Cimprich et al. 2022; Luthra et al. 2022) with a strong focus
62 on waste, byproducts or mine tailings (Asr et al., 2019; Ojeda-Pereira and Campos-Medina,
63 2021)(Ojeda-Pereira and Campos-Medina, 2021).
64 Phosphogypsum (PG) is the primary byproduct generated duringby the production of
65 phosphoric acid, an intermediate product in phosphate fertilizer production, from calcium
66 phosphate (apatite) ore. PG also exists in very small amounts in nature where it is the result
67 of natural guano processes as they took for instance place in the Cioclovina Cave located in
68 the Şureanu Mountains in Romania (Onac et al., 2002). Nearly 300 million t PG are produced
69 per year (Bouargane et al., 2023; Qin et al., 2023) of which 58% are dry- or wet stacked
70 (Fuleihan, 2012), 28% are discharged into coastal waters, and only 14% are reused
71 (Rutherford et al., 1994). It is also noteworthy that there are more than 3 billion t (estimates
72 in the literature usually range from 3-8 billion t) additional PG stacks worldwide (Chernysh
73 et al., 2021; Hermann et al., 2018; IAEA, 2013; Pliaka and Gaidajis, 2022; Tayibi et al.,
74 2009).
75 Specifically, PG is generated at the stage of wet-phosphoric acid (WPA) manufacturing at
76 which phosphate rock (pre-concentrated phosphate ore) is digested with sulfuric acid at
77 approximately 80 °C as shown in Eq. 1 and schematically in Fig. 1.
78 [𝐶𝑎3 (𝑃𝑂4 )2 ]3 𝐶𝑎𝐹2 + 10𝐻2 𝑆𝑂4 + 20𝐻2 𝑂 = 6𝐻3 𝑃𝑂4 + 10(𝐶𝑎𝑆𝑂4 2𝐻2 𝑂) + 2𝐻𝐹 (1)

79
80 Fig. 1: Overview and mass balance of phosphoric acid and phosphogypsum production
81 from phosphate rock with sulfuric acid.
82 The WPA process with sulfuric acid makes it possible to obtain PG in the form of a dihydrate
83 (CaSO4·2H2O) while other processes lead to the production of a hemi-hydrate

2
 84 (CaSO4·0.5H2O) or an anhydrite (CaSO4). The attack of one t phosphate rock is usually done
85 with 0.6 t of concentrated sulfuric acid that generates approximately 0.4 t of phosphoric acid
86 and 1.2 t of PG (Chang and Mantell, 1990; Hakim, 1997; van Selst et al., 1997).
87 The importance of calcium sulfate dihydrate (CaSO4·2H2O) in industrial and agricultural
88 fields as well as potential environmental risks associated with PG stacking (Tayibi et al.,
89 2009) and PG disposal in coastal waters (Aoun et al., 2015; Belahbib et al., 2021; Ben Salem
90 and Ayadi, 2017; Boudaya et al., 2019; El Zrelli et al., 2015; Jia et al., 2022) has increased
91 interest in considering PG no longer a waste, but a byproduct of WPA production that could
92 be utilized in construction to substitute natural gypsum (Aagli et al., 2005; Abu-Eishah et al.,
93 2000; Burnett et al., 1996; Cárdenas-Escudero et al., 2011; Elkanzi and Chalabi, 1991;
94 Haneklaus et al., 2022; Mulopo and Omoregbe, 2012).
95 In addition, phosphate ore can contain elevated concentrations of valuable trace elements in
96 the form of rare earths (Akfas et al., 2023; Cánovas et al., 2016; Chen and Graedel, 2015;
97 Emsbo et al., 2015; Ramirez et al., 2022) and uranium (Haneklaus, 2021). During WPA
98 production with sulfuric acid uranium largely (>80%) transfers to the phosphoric acid
99 product while the rare earths largely (>80%) transfer to the PG matrix (Rutherford et al.,
100 1994). Circular economy considerations in phosphate rock processing (Scholz and Wellmer,
101 2018), increased demand for uranium (Gabriel et al., 2013; Mudd, 2014) and rare earths
102 (Balaram, 2019; Liu and Chen, 2021), as well as geopolitical supply risks (Habib and
103 Wenzel, 2014; Jyothi et al., 2020; Mancheri et al., 2019) have spurred research investigating
104 potential rare earths recovery from PG (Cánovas et al., 2019; Kandil et al., 2010; Lütke et
105 al., 2022; Rychkov et al., 2018; Walawalkar et al., 2016) and techno-economic feasibility of
106 uranium recovery from WPA (Beltrami et al., 2014; López et al., 2019; Shang et al., 2021;
107 Tulsidas et al., 2019; Ye et al., 2019). Industrial processes for uranium recovery from WPA
108 are available and were used in the United States in the 1980s until decreasing uranium prices
109 made the practice unprofitable in the 1990s (Haneklaus et al., 2017b, 2017a; Kim et al., 2016;
110 Steiner et al., 2020). It is noteworthy that direct leaching approaches for rare earths and
111 uranium recovery from phosphate ore are also under investigation (Al Khaledi et al., 2019;
112 Banihashemi et al., 2021; Guzmán et al., 1995; Roshdy et al., 2023)(Al Khaledi et al., 2019;
113 Guzmán et al., 1995; Roshdy et al., 2023) and uranium concentrations in phosphate ore can
114 reach concentrations exceeding those of commercial uranium mines (Mwalongo et al., 2022).
115 If successful, direct leaching approaches could limit the radioactivity of PG considerably and
116 thus make the material available as a secondary raw material in construction.
117 Despite the interest in rare earth element (REE) recovery, PG still largely (about 96 wt%)
118 consists of gypsum. Depending on the type of the phosphate ore, traces of Cd, Zn, Pb, Hg,
119 Zr, Cu, Ba, REEs, Y, Th, U and 226Ra (which gives off 222Ra) are the most common and
120 relevant trace elements in PG. The radioactivity of the PG is usually 3-4 times higher than
121 that of the phosphate ore (Arhouni et al., 2022; Diwa et al., 2021; El-Bahi et al., 2017; Hakkar
122 et al., 2021; Qamouche et al., 2020)(Diwa et al. 2021; Hakkar et al. 2021; Arhouni et al.
123 2022). In Table 1 the radioactivity of PG is compared to concrete, ceramic bricks and natural
124 gypsum. While the values for 40K are smaller in the case of PG, the radioactivity for 266Ra
125 and 232Th can be 10 to 100 times higher than those of the conventional building materials.

3
126 Table 1. Radioactivity of PG compared with the radioactivity of some building materials.
Th αBq/kg
232
Index I=
Products 266
Ra αBq/kg Radon gas K γBq/kg
40
Thoron gas Ra/300+Th/200+K/3000
Concrete 25-50 20-50 200-1000 < 0,3
Bricks 50 15 600-1000 < 0,3
Natural gypsum 10-20 2-20 10-80 < 0,2
PG 100-2000 15-200 15-80 >1
127
128 During WPA production, PG usually settles in a slurry and the resulting acidic process waters
129 are recycled. The recycling of the process waters further concentrates the trace elements in
130 the PG and the material is acidic because of the acids involved in the WPA production
131 process. In addition, fluorine from the phosphate ore is also present.
132 During dry stacking of PG rainwater and remaining process waters can combine to form a
133 hydraulic head that forces the infiltration of the acidic stack water into underlying aquifer
134 systems or surrounding water bodies (Al-Hwaiti et al., 2010; Bituh et al., 2013; Borilo et al.,
135 2012; El Zrelli et al., 2019; Lysandrou and Pashalidis, 2008; Pérez-lópez et al., 2016; Pérez-
136 López et al., 2015; Zhou et al., 2023)(Borilo et al. 2012; Pérez-lópez et al. 2016). Besides,
137 fine dust from the powder-like PG stacks can be emitted causing respiratory problems
138 (Adeoye et al., 2021; Lütke et al., 2020; Silva et al., 2022)(Silva et al. 2022). As a result,
139 these wastes may be harmful to the environment and, in the long term, induce health problems
140 to local populations.
141 PG represents both an environmental problem and an opportunity for valuable secondary
142 resource recovery. Within the context of present-day regulations and circular economy
143 considerations, the only reasonable way to dealing with this material is the development of
144 sustainable practices for complete (zero-waste) utilization of PG.
145 Given the large amounts of PG tailings produced annually it is not surprising that a number
146 of researchers have already investigated and reviewed potential zero-waste strategies for PG
147 utilization (Bouargane et al., 2023; Cánovas et al., 2018; Y. Cao et al., 2021; Chernysh et al.,
148 2021; El-Didamony et al., 2013; Fornés et al., 2021; IFA, 2020; Kulczycka et al., 2016;
149 Mohammed et al., 2018; Qin et al., 2023; Rashad, 2017; Rosales et al., 2020; Saadaoui et al.,
150 2017)(El-Didamony et al. 2013; Rashad 2017; Saadaoui et al. 2017; Cánovas et al. 2018; IFA
151 2020; Cao et al. 2021; Chernysh et al. 2021; Bouargane et al. 2023; Qin et al. 2023)..
152 Although present in relatively small quantities by weight and volume the trace-elements
153 (particularly the radioactive ones) associated with PG are usually the limiting factor to zero-
154 waste PG utilization. The quantities of these trace-elements in the PG depends largely on the
155 phosphate ores processed and the chemical processes (usually it is the WPA process with
156 sulfuric acid) used for phosphoric acid production (Macías et al., 2017; Rutherford et al.,
157 1995)(Macías et al. 2017). A detailed knowledge of the trace-elements present in different
158 PG stacks is thus of profound interest when developing zero-waste PG utilization strategies
159 that should be applicable to a wide range of locations worldwide.
160 This critical review provides an overview of the physical-chemical properties of PG produced
161 from sedimentary and magmatic phosphate ore worldwide. Results from more than 25 years
162 of work on PG at École des Mines de Saint-Étienne (EMSE) are for the first time presented

4
163 together and critically discussed. In total PG samples from 67 industrial sites around the
164 world and PG samples synthesized under different conditions in the laboratory have been
165 considered. The large sample set allowed the authors to draw new conclusions with regards
166 to PG texture and morphology (Chapter 3.1), PG chemistry (Chapter 3.2), PG dehydration
167 (Chapter 3.3) and PG synthesis (Chapter 3.4) that led to an improved discussion on PG
168 circular economy considerations (Chapter 4).
169 2 Materials and methods

170 PG samples (67 in total) and phosphate rock samples for production of PG in the laboratory
171 were provided by different phosphoric acid and phosphate fertilizer producing companies
172 from around the world who anonymity was promised in exchange for samples. The samples
173 were usually dried at low temperature to reduce the humidity and then analysed shortly after
174 they were received. For this review we largely relied on the historic data and only analysed
175 samples again if we felt data was incomplete or inconclusive. When PG samples are stored
176 the samples humidity content can change. The storage, even over longer periods of time,
177 should not affect the concentration of major elements and minor trace elements. Gamma ray
178 spectroscopy was used for radioactivity measurements and inductively coupled plasma mass
179 spectrometry (ICP-MS) was used to determine the concentration of trace elements in the PG.
180 In addition, PG samples were analyzed using inductively coupled plasma optical emission
181 spectroscopy (ICP-OES), infrared (IR) spectroscopy, scanning electron microscope (SEM),
182 thermogravimetric analysis (TGA) and X-ray diffraction (XRD).
183 3 Results and discussion

184 3.1 PG texture and morphology

185 The texture of PG depends on the production process, the particle size distribution of the
186 phosphate rock (relative speed of H+, SO42- and Ca2+ ionization), the concentration of the
187 phosphoric acid in the reactor slurry (the higher reaction speed, the higher the ion mobility)
188 and the solid/liquid ratio. Hemihydrate processes operate with 3-5% lower solids content if
189 compared with dihydrate processes. According to (Bilal and Caspar, 2004) five
190 morphological groups can be differentiated and examples of these different groups are
191 provided in Fig. 21.

5
192
193 Fig. 21: PG types differentiated by their morphology and texture as rhombic type (Group
194 1), aggregate small rhombic type (Group 2), cluster type (Group 3), aggregate short needle
195 type (Group 4) and needle type (Group 5).

6
196 Group 1 is characterized by needle-shaped crystals with a uniform distribution of fine needles
197 and elongated platelets with sizes varying from 10 to 120 µm and crystallites typically
198 ranging from 400-550 nm. The predominant phases in this group are gypsum, bassanite and
199 traces of anhydrite. The needles tend to form monoclinic gypsum crystals. The particle size
200 distribution of the phosphate rock feed in this group is usually as following: 160 µm (20-
201 30%), 125 µm (30-40%), 80 µm (40-60%).
202 Group 2 is characterized by a texture of fine agglomerated needles that are 5 to 30 µm in size
203 and crystallites ranging from 70-300 nm. Group 2 shows some of the characteristics of natural
204 gypsum but the material is only agglomerated so that the cohesive forces, bonding the grains
205 together is weaker. The concentration of the phosphoric acid in the reactor slurry in this group
206 is usually as following: 30% P2O5 in phosphoric acid with 58.6% water. Further increasing
207 the P2O5 content to 40% P2O5 and 44.7% water or even 52% P2O5 and 28.2% water will lead
208 to smaller and more irregular crystallization of the PG.
209 PG of group 3 can be described as polycrystalline aggregates that are in a disorderly manner.
210 The crystals tend to form bunches that are sometimes referred to as "pink sand". The solid
211 content in the slurry (solid/liquid ratio) is usually 30 vol%, if thick rhombic crystals are
212 present or 22 vol% if needle type crystallization is given. The rhombic crystals are preferred
213 for better filtration. In this context it is noteworthy that hemihydrate systems typically operate
214 with 3-5% lower solids content than dihydrate systems.
215 The PG of group 4 differs significantly from the other groups. Here small grains are found
216 that typically have a roundish, pebble like shape. In direct contrast, the PG of group 5 consists
217 of very thin needle like crystals.
218 The texture of the PG is particularly important for its potential use as a building material. For
219 example, in the plaster industry only certain gypsum crystal sizes are acceptable to produce
220 plasterboards. Group 1, 2 and 5 are acceptable. On the other hand, group 3 and 4 cannot be
221 used for plasterboard production but could be utilized in the cement industry or in agriculture.
222 The texture and morphology also influence further processing of the PG in processes such as
223 calcination.
224 3.2 PG CHEMISTRY
225 Phosphate rock is a mineral resource that contains phosphorus and is used as the raw material
226 for the production of phosphoric acid, which is a key ingredient in fertilizer. It is mainly
227 found in marine sedimentary deposits, igneous rocks, and guano. Approximately 75% of the
228 global phosphate resources come from sedimentary phosphate rocks, while 20-25% are
229 obtained from igneous deposits (Manning, 2008; Ptáček, 2016; Pufahl and Groat, 2017).
230 Guano, despite its high phosphate content, cannot be used on a global scale as it is not
231 available in enough quantities (Pufahl and Groat, 2017).
232 Practically, phosphoric acid can be produced from phosphate ore through two main routes:
233 the wet process, which involves the use of strong mineral acids for decomposing of the
234 phosphate, and the dry process, where the ore is heated in an electric furnace to produce
235 elemental phosphorus as an intermediary (Abouzeid, 2008; Da Silva and Kulay, 2005). The
236 wet process, in which phosphate rock is usually treated with sulfuric acid, is the prevalent

7
237 way of manufacturing phosphoric acid today (Becker and others, 1989). This procedure leads
238 to the production of considerable amounts of hydrated calcium sulfate, commonly referred
239 to as PG (see simplified mass balance in Fig. 1). In accordance with the temperature as well
240 as the phosphate and sulphate content of the solution, either calcium sulfate dihydrate (DH),
241 hemihydrate (HH) or anhydrite (AH) is formed.
242 TIn fact, there are in fact two main wet processes that can be differentiated: single-stage
243 processes and recrystallization processes. Single-stage processes consist of only one
244 reaction-recrystallization step, regardless of the form of the obtained gypsum. The dihydrate
245 (DH) and hemihydrate (HH) processes are the two most prevalent methods in single-stage
246 procedures. The dihydrate (DH) process is widely used due to its simplicity and flexibility in
247 the treatment of different types of phosphate rock and is therefore considered a reliable
248 technique for phosphoric acid production on industrial scale (Abdelouahhab et al., 2022;
249 Abu-Eishah and Abu-Jabal, 2001; Houghtaling, 1973)(Houghtaling 1973; Abu-Eishah and
250 Abu-Jabal 2001). In this process, calcium sulfate in the form of gypsum (dihydrate: CaSO 4-
251 2H2O) is obtained at a temperature between 70 and 80 °C and moderate acid concentration.
252 The energy efficiency of the DH process is lower due to the requirement to finely ground
253 feed rock and theto resultingproduce a dilute phosphoric acid, which requires additional
254 energy for a subsequent concentration step. Phosphoric acid generated through the dihydrate
255 process is generally denoted as wet phosphoric acid (WPA). The Hemihydrate process (HH)
256 involves treating phosphate rocks at slightly higher temperatures (90-110°C) (De Vreugd et
257 al., 1994; Gioia et al., 1977; Jansen et al., 1984). The PG obtained by this method is
258 contaminated with heavy metals and radioactive elements. The HH technique has the
259 advantage of requiring less grinding, but, the recovery rate of P 2O5 is slightly lower (Abu-
260 Eishah and Abu-Jabal, 2001).
261 Recrystallisation processes are intended to enhance the efficiency of recovering P 2O5,
262 including the production of a purer final filter cake and, in some cases, generating a higher-
263 strength acid directly. These processes include hemihydrate-dihydrate (HDH), hemihydrate
264 dihydrate recrystallization (HRC), and dihemihydrate (DH/HH) routes (Gobbitt, 2012;
265 Koopman and Witkamp, 2000; Wang et al., 2021a, 2021b). In the HDH process, hemihydrate
266 (HH) is produced first and then filtered from the strong pure phosphoric acid product.
267 SubsequentlyThen, the HH is transformed into dihydrate (DH) through recrystallization,
268 leading to higher process efficiencies. The primary disadvantages of the HDH technique are
269 the corrosion caused by the higher temperatures in the reactors and the intricate nature of the
270 process, that places a strain on the operating staff. The HRC starts with the decomposition of
271 the phosphate rock under the same conditions as the hemihydrate process, but without
272 filtration. Then, the product undergoes recrystallization to form dihydrate and is finally
273 filtered to obtain the final product. This results in an acid with a slightly higher strength
274 compared to that produced by the dihydrate processes. Furthermore, this technique leads to
275 the formation of a pure dihydrate byproduct. The DH/HH process consists of formsing of
276 dihydrate (DH), which is filtered from phosphoric acid and then recrystallized to produce a
277 pure hemihydrate (HH) product. The HH product can be used directly in the production of
278 plasterboards. Over the last 20 years, the primary focus in WPA production has been the
279 reduction of the energy costs. Despite low energy consumption per kilogram of P 2O5

8
280 produced, the total cost is substantial due to high production rates. The most energy-intensive
281 step in the production of phosphoric acid, if the chemical and not the thermal route is chosen,
282 is associated with the grinding of the phosphate rock. In fact, the processes that can handle
283 coarser rock feeds (e.g., HH and HDH) have become more significant due to their overall
284 lower energy consumption. Table 2 shows the average composition of PG from different
285 industrial production processes. It is noteworthy that the individual production process
286 influences the PG texture and morphology that was discussed in the previous chapter. It is,
287 however, not possible to link the specific texture and morphology groups that were defined
288 earlier (Group 1-5) directly to the specific WPA processes listed in table 2.
289

9
290 Table 2. Average PG composition from industrial production.
Phosphate Rock Sedimentary Magmatic Mixed
Process HDH Hitashi HDH Hydro Agry DH Jacob DH Prayon (S) DH Prayon (M) HRC Kemira
Loss of ignition (1000 °C) 17.78% 20.65% 20.68% 21.10% 19.71% 20.72%
Combined moisture 12.74% 22.91% 16.31% NR NR NR
Purity (sample dried at 250 °C) 93.27% 94.87% 91.83% NR 95.56% NR
pH (5% solution in distilled
3.9 4.4 3.3 NR NR NR
water)
Major elements
CaO% 30.53% 33.65% 33.73% 35.20% 35.85% 36.42%
SO3% 44.83% 45.82% 42.50% 44.47% 43.49% NR
SiO2% 4.70% 6.82% 4.38% 5.13% 2.39% 3.25%
Al2O3% 0.08% 0.14% 0.36% 0.19% 0.36% ND
Fe2O3% 0.18% 0.06% 0.12% 0.18% 0.25% 0.03%
P2O5% 1.31% 0.28% 0.78% 0.52% 0.70% 0.38%
Soluble P2O5 0.23% NR NR 0.37% 0.08% 0.02%
Na2O% 0.06% 0.06% 0.08% 0.04% 0.07% 0.02%
K2O% 0.03% 0.02% 0.10% 0.01% 0.05% 0.02%
TiO2% 0.03% 0.02% 0.03% 0.03% 0.29% ND
MgO% 0.04% 0.07% 0.02% <0.01% 0.04% ND
MnO% 0.01% 0.01% NR <0.01% 0.01% ND
F% 0.55% 0.61% 0.64% 0.45% 0.55% 0.05%
Soluble F 0.21% 0.35% 0.11% 0.31% 0.24% 0.11%
CO2% 0.21% 0.56% 0.39% 0.35% 0.28% 0.12%
Organic C 0.01% 0.11% 0.05% 0.04% 0.02% 0.01%
Chloride as Cl 1.78 mg/L 1.86 mg/L 0.88 mg/L 2.4 mg/L NR NR
Nitrate 8.70 mg/L 6.83 mg/L 6.86 mg/L 10.02 mg/L NR NR
Trace elements
As NR NR NR 2 ppm NR NR
Co 1 ppm 1 ppm 1 ppm <1 ppm 5 ppm 1 ppm
Zn 49 ppm 48 ppm 34 ppm 44 ppm 14 ppm 8 ppm
Pb 6 ppm 2 ppm 2 ppm 4 ppm <1 ppm ND
Cd 1 ppm 2 ppm 2 ppm 3 ppm <1 ppm ND
Ni 3 ppm 2 ppm 1 ppm 4 ppm 1 ppm ND
V 4 ppm 2 ppm 4 ppm 2 ppm 7 ppm 1 ppm
Cr 4 ppm 5 ppm 7 ppm 14 ppm 4 ppm 3 ppm
Cu 9 ppm 60 ppm 1 ppm 33 ppm 5 ppm 10 ppm
Ba 76 ppm 109 ppm 150 ppm 53 ppm 207 ppm 39 ppm
Sr 569 ppm 801 ppm 402 ppm NR 7,692 ppm 2,099 ppm
Th 1 ppm 1 ppm 1 ppm 3 ppm 42 ppm 4 ppm
U 2 ppm 5 ppm 3 ppm <1 ppm 52 ppm 8 ppm
Rare earths (including Y)
Y 18 ppm 27 ppm 72 ppm 140 ppm 133 ppm 27 ppm
La 9 ppm 14 ppm 39 ppm 49 ppm 1,215 ppm 165 ppm
Ce 10 ppm 15 ppm 20 ppm 31 ppm 1,998 ppm 246 ppm
Nd 7 ppm 11 ppm 25 ppm 37 ppm 921 ppm NR
Sm 1 ppm 2 ppm 6 ppm NR NR NR
Eu < 1 ppm 1 ppm 1 ppm 2 ppm NR NR
Gd 1 ppm 2 ppm 7 ppm 10 ppm NR NR
Tb < 1 ppm <1 ppm 1 ppm 3 ppm NR NR
Dy 1 ppm 2 ppm 7 ppm NR NR NR
Ho < 1 ppm <1 ppm 2 ppm 2 ppm NR NR
Er 1 ppm 1 ppm 5 ppm 6 ppm NR NR
Tm < 1 ppm <1 ppm 1 ppm NR NR NR
Yb 1 ppm 1 ppm 4 ppm 8 ppm NR NR
Lu < 1 ppm <1 ppm 1 ppm 1 ppm NR NR
∑ REEs + Y 49 ppm 78 ppm 180 ppm 289 ppm 3,960 ppm 438 ppm
Radioactivity
226
Ra 211 Bq/kg 596 Bq/kg 414 Bq/kg 562 Bq/kg 267 Bq/kg NR
232
Th 5 Bq/kg <7 Bq/kg 5 Bq/kg 32 Bq/kg 185 Bq/kg NR
235
U <7 Bq/kg <16 Bq/kg 73 Bq/kg <9 Bq/kg 261 Bq/kg NR
40
K < 10 Bq/kg <26 Bq/kg 60 Bq/kg <12 Bq/kg NR NR
Radioacativity Index I 0.73 1.99 1.71 2.03 NR NR
291 NR: Not reported ; ND = not detected

10
292
293 Fig. 32: Distribution of PG (Magmatic PG and Sedimentary PG) in sum of REE versus Sr
294 diagram.
295 Generally, the PG samples produced from sedimentary phosphate rock (s-PG) have higher
296 SiO2 contents than the PG samples produced from magmatic phosphate rock (m-PG) with
297 the exception of Kola Peninsula PG samples that also have a high concentration of Na2O
298 (rock phosphate initials formed nepheline (Na3KAl4Si4O16)). The Y, Zr, Cu and Ba contents
299 are much higher in m-PG resulting from treatment of igneous apatite than in those from the
300 sulfuric treatment of sedimentary ores. Tunisian PG (an s-PG), for example, has relatively
301 high levels of Cd, Hg and Zn (Abbes et al., 2019; Choura, 2007; El Zrelli et al., 2015;
302 Rutherford et al., 1994). Approximately 80% of the Cd content passes preferably to the
303 phosphoric acid (Rutherford et al., 1994). If clean sulfuric acid is used, the major components
304 of the PG composition varies with the treatment of the phosphate rock while the trace
305 elements mainly depend on the origin of the ore. Macías et al. (2017) describe well how
306 sulfuric acid from pyrite roasting was used in the production of Huelva PG. This sulfuric acid
307 actually added a number of trace elements to the PG that did not result from the phosphate
308 rock itself. Radioactive elements, most notably 226Ra, 232Th, 40K result in the typical
309 radioactivity indexes (I = (Ra/300) + (Th/200) + (K/3000)) of 1.33 to 2.59 for s-PG and the
310 mixed PG (m-PG and s-PG). m-PG (particularly m-PG from Russia and some PG from
311 China) typically shows relatively low radioactivity indexes of 0.24 to 0.45. m-PG and also
312 mixed PG thus tend to show radioactivity indexes (I < 1) that theoretically allow for the use
313 of the material in construction as established by the International Commission on
314 Radiological Protection (ICRP) (Calderón-Morales et al., 2021; Campos et al., 2017;
315 Kuzmanović et al., 2021). In practice, the material is often not used since it is harder to sell
316 than a natural raw material that might show lower radioactivity, better strengths when
317 processed and pose much lower legal risks to producing companies that might have to adjust
318 to changing national regulations. Nevertheless, dDevelopments in PG treatment have been
319 made to further decrease the levels of radioactivity and impurities. The treatment methods
320 vary and may include washing, filtration, calcination, neutralization, leaching, and
321 purification, among others, to remove impurities and further reduce the radioactivity levels.

11
322 The specific process used depends on the composition of the PG and the required end use.
323 TNevertheless, the challengeproblem of resolving the crystallization of thorium nesosilicate
324 (ThSiO4), which is a highly radioactive substance, in m-PG remains unresolved though. The
325 radioactivity measurements on different sites have shown that fine particles are richer in
326 radon than fractions above 30 μm. Some PGs that were previously washed, showed a
327 decrease in levels of heavy metals, Th, REEs, P2O5, Na2O and K2O.

328
329 Fig. 43: Distribution of PG (s-PG and m-PG) in Chondrite normalized diagram.

330 The contents of major impurities in PG vary according to the process type used, while the
331 trace concentrations would depend directly on the nature of the initial phosphate rock
332 (Rutherford et al., 1994). Only As, Ba, Cd, Cr, Pb, Hg, Se and Ag are classified as toxic
333 elements by the United States EPA (Environmental Protection Agency). Their content in PG
334 is usually less than the tolerated limit though. The fate of major and trace elements in gypsum
335 can be attributed to many processes such as precipitation in a fairly pure mineral phase,
336 inclusions of liquids, co-precipitation, formation of solid solutions and surface adsorption of
337 organic compounds or minerals. Free phosphoric acid, unreacted phosphates, sodium
338 hexafluorosilicate, sodium sulfate, fluorosilicic acid H2SiF6 and organic compounds adhere
339 to the surface of the gypsum crystals.
340 PG may contain heavy metals (Burnett et al., 1996; Hamdona et al., 1993) such as Pb, Cd,
341 Hg, Zn and Cu (Al-Masri et al., 2004; Cossa et al., 2001; Garrido et al., 2005; Van Der Sluis
342 et al., 1986) with Cu usually being the most abundant one (117 ppm). The Cd (usually 1 ppm)
343 of the Syrian PG is in 45 to 58 µm fine fractions while most heavy metals (Cr, Co, Zr, Cu,
344 Pb, Z n, Ag, Ni, Cd and V) are found in the particle size fraction less than 20 µm (Rutherford
345 et al., 1996; Silva et al., 2005).
346 REEs (except Ce), Th and Ba are essentially in a residual phase which corresponds to a small
347 fraction of rock phosphate or monazite: (Ce, La, Nd, Th)PO4 and has insoluble compounds
348 such as phosphates and silicates (Santos et al., 2006). 60 to 80% of the REEs (especially the
349 light ones: La to Sm) present in the phosphate rock are found in the PG. In both the dihydrate
350 or hemihydrate process the heavy REEs (Gd and Lu) migrate into the phosphoric acid. REEs,
351 Y, Ba and Sr are typically found in the fine fraction (<20 µm) (Silva et al., 2005).

12
352
353 Fig. 54: Radioactivity index of PG (s-PG, m-PG and mixed phosphate PG) versus Sr
354 diagram.
355 The m-PGs have higher strontium and rare earths contents (La and Ce mainly but also Pr,
356 Eu, Dy, Er and Lu) than s-PGs. In this work iIt was possible to draw a border zone, where
357 the Sr/Ca ratio is approximately 0.0057 (Sr/Ca <0.0057 = s-PG and Sr/Ca> 0.0057 = m-PG)
358 (Bilal et al., 2010).
359 Lanthanides retard the growth rate of gypsum crystals on all sides (preferably that with miller
360 indices (011) of needles for cerium) except for (-111) (Ce3 +> La3+> Eu3+> Er3+) because the
361 ionic radius of lanthanides such as cerium (128pm) is closer to that of calcium (126pm) than
362 lanthanides such as erbium (114pm)) (Koopman and Witkamp, 2002). In addition, Ce3+ and
363 Na+ form a solid solution with the hemihydrate during crystallization [(Na,Ce)(SO4)2.H2O +
364 CePO4.0,5H2O] – CaSO4.0,5H2O. This stabilizes the structure of the hemihydrate and slows
365 down the recrystallization of the dihydrate (Rutherford et al., 1994).
366 The other elements which can be substituted in the structure of the gypsum are Cd, Sr, Mg,
367 Na, K, Cl and Se. Cd2+ ions can replace Ca2+ ions because they have the same charge and
368 very similar ionic radii (1.12A and 1.07A respectively). The incorporation of Cd2+ increases
369 with increasing H2SO4 (Rutherford et al., 1994).
370 The s-PGs usually have higher SiO2 contents than the m-PGs with the exception of the PG
371 produced from phosphate rock from the Kola Peninsula (Russia) (a m-PG that also has high
372 Na2O contents because they are made up of nepheline (Na3KAl4Si4O16)). Silica exists as
373 amorphous SiO2, quartz or SiO2-containing minerals (Elkanzi and Chalabi, 1991; Rutherford
374 et al., 1994). The selenium may be found in the form of CaSeO4.2H2O in the PG (Kruger and
375 Abriel, 1991). Fluorides precipitate in the form of complex crystalline salts, depending on
376 the concentrations of Al, Si, Mg, Na, Ca and sulphates dissolved in the acid. The most
377 common are calcium fluorosilicate and calcium fluoride. During the process of
378 manufacturing phosphoric acid, silicon would increases the growth of the gypsum crystals
379 along the c axis and prevent the formation of aggregates because it tends to dissolve fluorine,
380 which does not syncrystallize in the PG. This therefore shows normal acicular growth.

13
381 Aluminum and silica tend to form complexes with fluorides and therefore modify the
382 distribution of ionic species (6F- = SiF2-6 or AlF2-6). When the alkali concentration is low,
383 then chukhrovite: Ca4(SO4)(AlF6)SiF6).12H2O (whose structure has been described by
384 (Mathew et al., 1981) can precipitate. For high dissolved aluminum concentrations, fluorine
385 precipitates in the form of cryolite: (Na, K)3AlF6. The presence of magnesium changes the
386 fluorine precipitation mechanism. Specifically, the MgSiF6.6H2O phase appears. This group
387 of fluorosilicates crystallize in acicular form, which helps to improve the filterability of
388 calcium sulphate. When F, Mg, Na and Al are present, ralstonite: NaxMgxAl2-x (F, OH)6H2O
389 (x between 0.2 and 1.0 and the F/OH molar ratio between 3 and 1) is frequently formed (Lehr
390 et al., 1966). Fluorite and fluorapatite may be the solids controlling the solubility potentials
391 of fluorine in PG. The study of the PO4-SiO2-F system has shown an interdependence
392 between PO43- and F- because they are surely associated with the same phase, apatite
393 [Ca5(PO4, CO3)3(F, OH)2] which reprecipitates between F- and SiO2 because they would form
394 an alkaline hexa-Fluorosilicate (Na, K)2SiF6 (Burnett and Elzerman, 2001). The length/width
395 ratio (L/l) varies depending on the impurity present in the PG. Indeed, the presence of
396 fluorides (up to 2.09-2.80% in F-) or SiO2 (0.9-3.0%) leads to an increase of L/l while this
397 ratio remains unchanged with impurities such as CO2 (1.5-4.6%) and Fe2O3 (0.17- 0.48%) or
398 decreases slightly with Al2O3 (0.15-0.40%).
399 Dicalcium phosphate, monosodium sulfate and fluorophosphate can also enter the structure
400 of gypsum. A solid solution exists between the dicalcium phosphates because the HPO42-
401 ions replace the SO42- ions in the gypsum structure because these 2 ions have the same size,
402 molar mass and charge (Van Der Sluis et al., 1986). This substitution of phosphates in the
403 gypsum network during acidification is reduced with a high concentration of sulphates,
404 longer attack times of the phosphate rock, higher reaction temperatures and a large
405 percentage of solids. The incorporation of HPO42- decreases when H2SO4 increases. HPO42-
406 ions can be incorporated into the gypsum structure thus forming ardealite Ca(SO4)1-
407 x(HPO4)x.2H2O where x= 0.5 (Freyer and Voigt, 2003). One method to differentiate PG from
408 synthetic gypsum is for instance thewould be to analyzeanalysis them by IR spectroscopy.
409 PG as an additional band at 840 cm-1 relating to the absorption of the H2PO4 group (Hanna
410 et al., 2009) that cannot be observed in case of synthetic gypsum (Sebbahi et al., 1997).
411 El Moussaouiti et al. (1996) observed the appearance of a band at 836 cm-1 generated by
412 phosphate ions and the increase in intensity of that at 1094 cm-1 corresponds to the
413 superposition of the vibrations of SO42- and HPO42-. It was then provend (Guilhot et al., 1974)
414 that by IR spectroscopy, it is possible to highlight the syncrystallized HPO42- ions (836 and
415 1015 cm-1), HPO42- from the brushite phase (872 cm-1) and syncrystallized FPO32- (766 and
416 1025 cm-1). They can be measured (the heights of these bands depend on the content of
417 syncrystallized ions) (Guilhot et al., 1974). Gypsum crystals were observed to be needle-like
418 as long as the molar fraction of syncrystallized HPO42- ions does not exceed 0.07 to 0.085.
419 Beyond this value, the products appear in the form of lamellae groups in flower-like forms
420 (Guilhot et al., 1974). EDS analyzes (energy dispersive spectroscopy) do not show the
421 presence of phosphorus in PG (El Moussaouiti et al., 1996).
422 The complexes containing the AlF2-5 ions retard the growth of gypsum crystals because they
423 replace the SO42- ions and are mainly adsorbed on the faces (011) and (-111) hence a decrease

14
424 in the L/l ratio of the crystals can be observed. The presence of aluminum fluorides causes
425 also the formation of small agglomerated crystals, having a hexagonal structure (Koopman
426 and Witkamp, 2002; Martynowicz, 1994; Martynowicz et al., 1996a, 1996b). From the Al
427 content of the phosphate rock and the values of the aluminum distribution coefficients, it is
428 possible to know the aluminum concentration during the hemihydrate process and the
429 probability that difficult to filter dihydrate crystals are formed. The applicability of different
430 phosphate rocks, in terms of their Al content, can be determined (Martynowicz et al., 1996b).
431 The hemihydrate obtained by calcining gypsum containing this co-crystallized species has a
432 setting-time which is less easy to control by adding a setting retarder than the pure
433 hemihydrate (Kitchen, 2007). During the phosphoric acid manufacturing process, the
434 presence of aluminum limits the growth of gypsum along the c-axis and promotes the
435 formation of aggregates. The presence of carbonates can lead to the formation of
436 rapidcreekite (Ca2(SO4)(CO3)4H2O) (Dydo et al., 2003).
437 3.3 PG DEHYDRATION
438 Efforts should focus on impurities, which play an important role in the hydration of PG to
439 use as substitutes for natural gypsum. Indeed, the s-PG shows conductometric curves highly
440 variable and late stabilization of conductivity (2.9 mS/cm) after 16 minutes and up to 32
441 minutes. Some of the s-PGs are characterized by a late conductivity stabilization, greater than
442 40 minutes and the conductivity at a high value of 4.1mS/cm. Some of S-PGs can further be
443 characterized by a late conductivity stabilization, greater than 40 minutes and the
444 conductivity at a high value of 4.1mS/cm.
445 The S-PG has impurities that slowly release and can result in an increase of the setting time
446 (Fig. 65). The conductivity stabilization time (setting time) reduced after many washings of
447 s-PG prior to dehydration. Experimental work in the EMSE laboratory (Bard and Bilal, 2011;
448 Bilal et al., 2014; Bourgier, 2007; Laborde, 2002) showed that the hydration depends mainly
449 on the presence of P2O5 in the PG, which was also confirmed more recently by others (see
450 for instance (Jia et al., 2021; Liu et al., 2020)). This effect disappeared when heating the PG
451 at 160 °C during which a reversal of the conductometric curves could be observed with
452 significant reduction of the setting time (Fig. 65). Excellent work on this was also carried out
453 by (Geraldo et al., 2020) for PG from Brazil as well as (Cao et al., 2022; W. Cao et al., 2021)
454 and (Li and Zhang, 2021) for PG from China. The relatively low required temperatures lead
455 to first experiments to consider waste heat (Mittal and Rakshit, 2020) or solar power (Palla
456 et al., 2022) for treatment of PG. Experimental laboratory studies have also shown that a
457 treatment consisting of washing with dilute citric acid solutions (Singh, 2002), oxalic acid
458 solutions (Cai et al., 2021) or sulfuric acid solutions (Bilal et al., 2014, 2010) helped reducing
459 soluble P2O5 in the PG considerably (Bilal et al. 2010, 2014).

15
460 Fig. 65: Conductometric curves of different PGs and stabilization time of conductivity
461 (setting time).

462 3.4 PG SYNTHESIS

463 To better understand the morphology, texture, and presence of impurities in PG various
464 syntheses of PG and gypsum were carried out. The first lesson learnt is that the composition
465 and morphology depend essentially on the starting composition of the phosphate ore and the
466 concentrations of the sulfuric acid during the acid attack and the washing that follows. During
467 the acid attack little mobile elements are found in or with the PG such as P2O5 and F in solid
468 or dissolved form as: Ca (H2PO4).2H2O, Ca3PO4, CaF2, CaHPO4.2H2O (brushite),
469 CaFPO3.2H2O; and HPO42-, FPO32- ions and AlF52- (Kitchen, 2007; Martynowicz et al.,
470 1996a) co-crystallize in PG. Dduring washing, several salts and acids are not completely
471 eliminated (H2PO4-, SiF6- or F-, Na+ and K+).
472 The excess of sulfuric acid and temperature in the acid attack plays an important role on the
473 texture and morphology of the PG that has already been discussed in Chapter 3.1 and is
474 further illustrated in (Fig. 76). The excess sulfuric acid in the reactor slurry is the most
475 effective factor governing the quality of the crystallization. With very low sulfuric acid
476 content, only small diamond-like crystals awere produced (Bard and Bilal, 2011). As the
477 sulfate levels increase, the crystal size increases and the shape of the crystals stretched out
478 most of the time, eventually becoming needle-like. The level of sulfuric acid is also
479 responsible forlated to the syn- or co-crystallization of the P2O5.

16
 H2SO4 C = 15% C = 20% C = 30%
25°C

100µm

100µm

70°C

20µm

90°C

20µm
480
481 Fig. 76: Variation of the texture of the gypsum according to the content of H2SO4 and the
482 temperature.
483 The crystal structure of brushite is similar to that of gypsum despite not being isostructural.
484 Both minerals belong to the monoclinic system, but they have different space groups (Cole
485 and Lancucki, 1974; Curry and Jones, 1971). This similarity makes the investigation of the
486 brushite-gypsum system by XRD challenging. In fact, the intense peaks that correspond to
487 the reflexion 020 (2θ = 11.7°) of brushite and gypsum are indistinguishable (Roode-Gutzmer
488 and Strydom, 1999). However, to differentiate these two phases the peaks at 2θ = 20.7° for
489 gypsum and 2θ = 21.0° for brushite should be considered. The two peaks are only discernible
490 for brushite contents greater than 1% in the gypsum and brushite mixture.
491 On the other hand, XRD analysis can reveal the presence of a new phase, ardealite
492 (Ca2(SO4)(HPO4).4H2O) when the phosphate ion content is above 7% (Fig. 87). For HPO42-
493 contents between 40% and 55%, the gypsum disappears and only the ardealite
494 (Ca2(SO4)(HPO4).4H2O) phase remains. For HPO42- contents between 55% and 95%,
495 ardealite coexists with brushite but beyond that only brushite is present. Rinaudo et al. (1994)
496 obtained the same order of appearance of the phases according to the variation of the contents
497 of HPO42- but they did not see the demixing of ardealite into ardealite and brushite after 55%
498 of the ion HPO42- the demixing of ardealite into ardealite and brushite.
499 In fact, the dehydration of brushite is less known than that of gypsum. Figure 98 highlights
500 the behaviour of brushite when it has been calcined at different temperatures. For
501 temperatures between 25 and 250˚C, only the brushite CaHPO4.2H2O and monetite CaHPO4
502 phases were observed. At 250° C, the initial brushite transformed into monetite after losing
503 its structural water. The Ca3(PO4)2 and Ca(H2PO4).H2O phases were not detected by XRD.
504 According to Lang Dupont (1985), it is impossible to obtain pure anhydrous calcium

17
505 phosphate since before total dehydration, calcium pyrophosphate Ca2P2O7 begins to form.
506 There is always a superposition of the two reactions. During the dehydration of the gypsum-
507 brushite mixtures, the transformation of anhydrite III into anhydrite II occurs at higher
508 temperatures than for pure gypsum. The brushite present in the mixture is transformed at 150
509 °C in two phases (Fig. 109): 24% brushite and 76% monetite (semi-hydrated phase). This
510 brushite differs from the first by its physicochemical characteristics.
511
512
Ca (SO )(HPO ).4H O

Ca (SO )(HPO ).4H O

).4HOO
4 O2

2 2

2
Ca2SO4)(HPOH4)4H2O

CaHPO .2H O

CaHPO .2H O
2

513
.2H O

(SO )(HPO)4H
.2H O

)4H

CaHPO42H24O 2
CaHPO42H24O 2
4 2

4 2

44

4
42H2O

42H2O

514
2 4)(HPOH
2 )(HPOH

+
+
CaSO

CaSO

515
CaSO

CaSO

4
4

2SO
Ca2SO

516
2
CaCa

517
518

Brushite
Brushite
brushite

brushite
ardéalite
Ardealite

ardéalite
Ardealite
Ardealite
ardéalite
Gypsum
gypse

gypse

519
Gypsum

+
+

520
521 2- 2-
SO
SO4 2- HPO4 2-
HPO
522 4 4
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
523
524
525 Fig. 87: Order of appearance of the phases (XRD analyzes) as a function of the variation in
526 the HPO42- contents.

18
 brushite Prolabo [001]

CaHPO4.2H2O
Ca2P2O7
CaHPO4
600 °C
450 °C
350 °C
400
Lin (Counts)

300 250 °C
200 °C
200 175 °C
150 °C
125 °C
100
100 °C
0 25 °C
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

527 2-Theta - Scale

Temp.: 25 °C (Room) X + 19.2 mm - Y + 42.0 mm - Temp.: 450 °C
X + 3.2 mm - Y + 7.0 mm - Temp.: 100 °C X + 22.4 mm - Y + 49.0 mm - Temp.: 600 °C
528 Fig. 98: A series of XRD patterns taken during
X + 4.8 mm - Y + 10.5 mm - Temp.: 125 °C
the calcination of brushite
X + 6.4 mm - Y + 14.0 mm - Temp.: 150 °C

529 X + 8.0 mm - Y + 17.5 mm - Temp.: 175 °C

X + 9.6 mm - Y + 21.0 mm - Temp.: 200 °C
X + 12.8 mm - Y + 28.0 mm - Temp.: 250 °C
530 X + 16.0 mm - Y + 35.0 mm - Temp.: 350 °C

531
Bassanite + Monetite + Brushite
Bassanite + Brushite + Monetite

Brushite + Monetite + Bassanite

Brushite + Monetite +
(Bassanite)
Bassanite

CaSO4 CaHPO4

532 0 50 100
533 Fig. 109: Phases present in the CaSO4.2H2O - CaHPO4.2H2O system heated to 150 °C
534 determined by XRD.
535
536

19
537 In situ XRD analysis revealed that ardealite (Ca(HPO4)(SO4).4H2O) was decomposed during
538 heat treatment into brushite (CaHPO4.2H2O), monetite (CaHPO4) and bassanite
539 (CaSO4.0,5H2O) (see Fig.110). At a temperature above 150 °C, the bassanite was
540 transformed into anhydrite III, while at 250 °C, brushite was entirely replaced by monetite.
541 Subsequently, between 250˚C and 350˚C, the appearance of stable anhydrite II CaSO4 and
542 amorphous calcium pyrophosphate Ca2P2O7 had been observed. This explanation of the
543 dehydration of ardealite is consistent with that of Balenzano et al. (1984) and Secco et al.
544 (2015).
545
546

547
548 Fig. 110: A series of XRD patterns taken during the calcination of ardealite.
549 The infrared absorption spectra of the gypsum-brushite mixtures are shown in Fig. 121 and
550 the characters and intensities of the absorption bands obtained on the different gypsum and
551 brushite mixtures are given in Table 3. The band assignments are in agreement with the work
552 of (Dumitras et al., 2004) which was based on the work of (Berry and Baddiel, 1967; Murat
553 and Foucault, 1977; Petrov et al., 1967; Tortet et al., 1996; Trpkovska et al., 1999). Infrared
554 absorption spectra of the mixture containing 50% gypsum and 50% brushite (CaHPO4.2H2O)
555 show the characteristic bands of gypsum and brushite. They are very different from those of
556 ardealite (Ca2(SO4)(HPO4).4H2O). IR can thus be used as a relatively easy method to
557 distinguish the mechanical mixtures of gypsum-brushite of a phase of the ardealite type
558 containing in equal proportions HPO42- and SO42-.

20
559 Table 3: Ssummary of the waves corresponding to the absorption bands of HPO42-
560 observed on the infrared spectra of solid solution gypsum and of the gypsum-brushite
561 mixture.
Characteristic bands of HPO42- wavelengths (cm-1)
HPO42- (Brushite) 1650 986 872 524
HPO42- syn-crystallized 1017 836
562

563

10%

40%

50%

564

565 Fig. 121: Infrared absorption spectrum of a solid solution as a function of the contents by
566 weight of CaHPO42H2O / CaSO42HO + CaHPO42H2O) = 5, 10, 12, 13, 15, 20, 30, 40 and
567 50.

568 Brushite in a gypsum-brushite mixture, is detectable in the infrared spectrum by the

569 absorption band 872 cm-1 (see Fig. 121) corresponding to the vibration of symmetrical
570 valence stretching P-O(H) of the structural HPO42- group. If the gypsum-brushite mixture is
571 homogeneous, it is possible to relate it to the height of this absorption band and the amount
572 of brushite introduced (Aslanian et al., 1980).
573 In a solid solution with 5wt% HPO42- only the band at 837 cm−1 is present (see Fig. 121),
574 representing the syncrystallized phosphate ion HPO42-, while the band at 872 cm−1 appears at
575 10wt% HPO42- in the solid solution corresponds to the demixing of the solid solution gypsum
576 (SO42-, HPO42-) into two gypsum phases (HPO42- syncrystallized) and ardealite Ca(SO4)1−
2- −1
577 x(HPO4)x2H2O. At 40-50 wt% HPO4 only the 872 cm band remains which corresponds to
2-
578 the HPO4 ion of ardealite.

21
579 The IR studies of gypsum samples containing varying amounts of HPO42- showed that the
580 primary absorption band of syncrystallized HPO42- ions, found at 836 cm-1, increased in
581 intensity until it reached a P/S ratio of approximately 0.1111 (see Fig. 132). However, as the
582 proportion of inserted phosphate ions continued to rise, the intensity of the absorption band
583 decreased and eventually disappeared when the P/S ratio reached 0.4287. Simultaneously,
584 the characteristic absorption band of ardealite appeared for P/S = 0.1111 at 864 cm-1. The
585 intensity of this band raised with an increase of the P2O5 percentage and gradually shifted to
586 higher wavelengths. For P/S ≅ 4, the absorption band was found at 870 cm-1, and it shifted
587 to 872 cm-1 for pure brushite. Therefore, it wasis impossible for us to establish a limit between
588 the passage from the ardealite phase to the brushite phase usingby this analysis technique. In
589 this spectral range, Aslanian et al., (1980) had only identified two absorption bands: the band
590 at 850 cm-1 which appeared for a P/S = 0.080 but was not attributed, and the 872 cm-1 band
591 identified for a P/S ratio above 0.25. Similarly, Rinaudo and Abbona, (1988) also found that
592 the spectrum of synthetic ardealite is different from that of a mixture of gypsum and brushite.
593 However, they have not mentioned the presence of the 864 cm-1 absorption band. It would
594 be interesting to analyse in more detail the part where HPO42- > 96%. Contrary to the HPO42-
595 < 3% area, the characteristic absorption bands of HPO42- (SO42- ions substituted by HPO42-)
596 in the gypsum phase that can bewas observed relatively easily, then it seems difficult to
597 determine the absorption bands relative to SO42- ions in the brushite lattice, considering the
598 observations made above. We were indeed not able to observeIndeed, there would be ano
599 new absorption band but only a shift of the band located at 872 cm-1 relative to the brushite.
600 In the spectral range from 500 to 700 cm-1, it was observed that as the amount of P2O5
601 increased, the absorption band characteristic of syncrystallized HPO42- ions located at
602 527 cm-1 intensified and shifted to 517 cm-1, a band attributed to pure brushite (see Fig. 132).
603 Moreover, for P/S=4, the bands at 668 and 597 cm-1 disappeared and a new absorption band
604 at 576 cm- 1 could behas been observed.
605 The solid solution containing HPO42- syncrystallized ions wasis characterized with respect to
606 the gypsum-brushite mechanical mixture by the presence of two absorption bands: 1017cm-
607 1
corresponding to the ν3 vibration of asymmetric valence stretching P-O(H) of the structural
608 group (PO4)3- and 837 cm-1 vibration linked to the structural group HPO42- the latter is on
609 average twice as important. It can be noted that there is a very good correlation between the
610 quantity of syncrystallized HPO42- ions introduced into the solid solution gypsum and the
611 height of the peak of the absorption band (Fig. 143). If the gypsum-brushite mixture is
612 homogeneous, it is possible to relate the height of this absorption band to the amount of
613 brushite introduced (see Fig. 143) (Aslanian et al., 1980; Bard and Bilal, 2011; Bilal et al.,
614 2014; Bourgier, 2007; Dumitras et al., 2011, 2004; Laborde, 2002; Marincea et al., 2004).

615

616

617

618

22
619
620 Fig. 132: Infrared spectra of gypsum samples containing 0.00% < HPO42- <100.00% A Formatted: Fo
621 and B) 700-950 cm-1 C and D) 500-700 cm-1.
622 CaSO4.2H2O, P/S = 0.0526, 0.1111, 0.1364, 0.1494, 0.1522, 0.2500 (Figs. A and C)
623 CaSO4.2H2O, P/S = 0.1111, 0.2500, 0.4287, 0.6666, 1.0000, 1.5000, 4.0000, CaHPO4.2H2O (Figs. B and D)
624
625
Peak height 837cm (% transmittance)
2 3
-1

0 1

0 0.5 1 1.5 2 2.5 3

CaHPO42H2O / (CaSO42H2O + CaHPO42H2O)
626

627 Fig. 143: Correlation between the height of the 837 cm-1 absorption band and the content Formatted: Fo
628 of HPO42- syncrystallized ions. Formatted: Fo

23
629

-5

-10 Ardealite
Heatflow (mW)

-15

-20

-25
Gypsum
-30
Brushite
-35
0 100 200 300 400 500 600
Temperature (°C)
630
631 Fig. 154: Dehydration of the pure gypsum (blue), brushite (red) and ardealite (green)
632 phases.
633 During the dehydration of synthetic PG, the transformation of anhydrite III to anhydrite II
634 occurs at higher temperatures than for pure gypsum. The brushite present in the mixture is
635 transformed at 150 °C in two phases (Fig. 154): 24% brushite and 76% monetite (semi-
636 hydrated phase). On the DSC curve an endothermic effect can be observed at 156°C and
637 199°C corresponding to the departure of molecular water. The work on synthetic brushite by
638 (C. Rinaudo and Abbona, 1988; Sivakumar et al., 1998) agree with our observations on thise
639 double endothermic effects.
640 The mass loss in the first step is 4.11% corresponding to weakly bound molecular water and
641 the second mass loss is 16.42%, or 20.53% of the total cumulative mass loss. The third mass
642 loss of 4.81% at 415 °C corresponds to the disappearance of monetite and the formation of
643 Ca2P2O7 corresponding to the exothermic peak on the DSC curve (Fig. 165).
644 The dehydration of ardealite occurs in several stages with endothermic peaks at 135 °C, 165
645 °C, 190 °C and 215 °C (C. Rinaudo and Abbona, 1988) and results in a total mass loss of
646 about 20%.
647

24
648

Solid solutions

8
Delay of hydration
7
Conductivity (mS/cm)

6 After cooking PG
5

4 1.50% Syn- or Co–crystallized P 2O5

3

2 0.25%
1
Setting time
0
0 10 20 30 40 50 60
Tim e (min)

649

650 Fig. 165: Conductometric curves and stabilization time of conductivity (setting time) of
651 synthetic PG with different P2O5 contents and hydration of synthetic PG cooking.

652

653

654 4 PG circular economy considerations

655 The extractive nature of mining does not enable the raw material industry to become fully Formatted: Lin
656 circular. In other words, the nature of mining will unavoidably make it environmentally between Latin a
text and numbe
657 disruptive (Schoenberger, 2016; Zhao et al., 2012). There is still plenty of room for the
658 mining industry (de la Torre de Palacios and Espí Rodríguez, 2022; Gorman and Dzombak,
659 2018; Laurence, 2011; Littleboy et al., 2019; Whitmore, 2006), and also the phosphate ore
660 mining industry (Geissler et al., 2018) to become more sustainable though. The extractive
661 industries surely are part of the economy, providing the raw materials for all other activities,
662 and they will therefore also be a part of any envisioned circular economy (Lèbre et al., 2017a;
663 Singh et al., 2020). Circular economy considerations in mining usually focus on minimizing
664 the environmental impact during raw material extraction (Input in Fig. 17) and minimizing
665 the quantity as well as the environmental impact of the produced waste (Output in Fig. 17)
666 (Cimprich et al., 2022; Gedam et al., 2021; Luthra et al., 2022; Tayebi-Khorami et al., 2019).
667 There is a fine, and we like to think permeable, line between what is a waste and what might
668 be a resource (Lèbre et al., 2017b). This is even more true for naturally occurring radioactive
669 material (NORM) or technologically enhanced NORM (TENORM) such as PG that are often
670 overlooked in circular economy considerations (Tsioka and Voudrias, 2020; Turcanu et al.,
671 2022). Figure 17 provides a simplified illustration of our understanding of the circular
672 economy with considerations for fresh- and stacked PG. Specifically, we believe that fresh
673 PG should ideally not be considered a waste but be processed and thus stay within the circular
674 economy consisting of production, consumption, and recycling in Fig. 17 (Xu et al., 2019).
675 The considerable quantities of stacked PG (3-8 billion t worldwide) can also be processed

25
676 and thus added to the circular economy, minimizing raw material extraction, for instance for
677 natural gypsum and rare earths, elsewhere.

Formatted: Ce

678
679 Fig. 17: Circular economy considerations for PG.
680 Policies to support the re-use of PG as illustrated in Fig. 17 are already underway (Cui et al.,
681 2022) and we sincerely hope that this review will add knowledge that can further foster the
682 utilization of fresh and stacked PG as a valuable secondary resource. This practice would not
683 only reduce environmental risks associated with storing PG by free a considerable amount of
684 land that can then be used for other purposes.
685 This work allowed us to compare a relatively large number of PG samples with one another
686 and learn about the different national practices and regulations in the process. It is challenging
687 to draw generally applicable conclusions from such a large dataset. (Kinnunen and Kaksonen
688 2019; Tayebi-Khorami et al. 2019; Upadhyay et al. 2021; Cimprich et al. 2022; Luthra et al.
689 2022)We are confident to share though that dDirectly marketable PG needs to fulfill strict
690 specification that usually depend on its free moisturemoisture content, total P2O5 content,
691 soluble and insoluble P2O5 content, the PG insoluble F and soluble F content, pH, the particle
692 size, morphology, texture, and radioactivity index. The chapters of this review were in fact
693 designed accordingly to add our experience about PG analysis and processing. This
694 experience also showed that Simple washing with diluted sulfuric acid, morphological and
695 chemical characterization can be simple but powerful methods to identify marketable PG.
696
697 Table 4 provides an example of the PG specifications required for the plaster industry that
698 we consider to be one of the most important takers of fresh and stacked PG worldwide. In
699 this context, it is noteworthy that in case of fresh PG The PG recovery depends essentially
700 on a changes in the current phosphoric acid production processes (using appropriate contents
701 of sulfuric acid use, the temperature of the reaction, the particle size of the phosphate rock
702 and a mixture of different types of magmatic and sedimentary phosphate rock to influence

26
703 thefor morphology and texture of the PG) can have significant effects on the resulting PG
704 stocks.
705 As of now the phosphate fertilizer industry designs the phosphoric acid production processes
706 with the aim of producing the best fertilizers (as they should). Not at all considering or having
707 to consider the quality of the produced PG, can however, result in PG that is a particularly
708 hard sell. We sincerely hope that this one-product-thinking will change to a multi-product- Formatted: Fo
709 thinking as part of which the quality of both phosphoric acid and PG are considered in the
Formatted: Fo
710 process designs, so that both can later be sold at ease.
711 Simple washing with diluted sulfuric acid, morphological and chemical characterization can
712 be powerful methods to identify marketable PG.
713 Table 4: Specification of PG for use in the plaster industry.
Free Moisture % If possible <15
Total P2O5% <1
Insoluble P2O5% <0.6
Soluble P2O5% <0.05
Co-crystallized P2O5% < 0,5
Total F <1
Insoluble F% <0.6
Co-crystallized F < 0,15
Soluble F% <0.05
Na2O % < 0,5
MgO % < 0,6
Chloride < 0,01
pH 5< pH < 8
SiO2 (quartz & non soluble in HCl acid) < 1,25%
PARTICLE SIZE: d50 50 µm < d 50 < 100 µm
No needles, no spherical shapes
RadioactivityIndex I = Index for final product < 1
Ra/300+Th/200+K/3000
Additives None which can penalize setting times
Size specification for shipping Pellets 20/30mm or <70mm
Size specification for utilization Mixed with clinker then ground
714
715

716
717 5 Conclusions and outlook

718 This critical review summarized over 25 years of work on PG utilization at EMSE. PG
719 samples from more than 657 storage sideslocations were considered and novellarger
720 conclusions on s-PG and m-PG, as well as how the processing parameters of these PGs define
721 the PG composition are provided. Besides, the critical review puts an emphasis on providing
722 useful observation for PG analysis and introduces an important way to group PG samples by
723 its texture and morphology that is particularly relevant if PG is investigated for potential use
724 as a construction material. Although a relatively large set of samples was used in this critical
725 review tracing the PG back to the raw material utilized was sometimes challenging as

27
726 industrial samples were used and the companies providing them had an interest to not fully
727 disclose processing as well as mixing parameters. Future studies should aim for more
728 transparency and also more consistency with regards to sample analysis and comparison so
729 that further conclusions, relevant for the utilization of PG can be drawn. Recycling of PG is
730 an extremely active topic and we provided novel, higher-level analysis of the role of fresh
731 and stacked PG in an envisioned circular economy.
732 Ethical Approval
733 Not applicable.
734 Consent to Participate
735 Not applicable.
736 Consent to Publish
737 Not applicable.
738 Authors Statement
739 Conceptualization, Methodology, Writing-Reviewing and Editing: EB; Writing-Reviewing
740 and Editing: HB, NH; Reviewing and Editing: VB, HM, DGD, FB, ML, JPC, BG, LI, MB,
741 MAI, SM, ME, BL, RRD, JDR, YC, VC, HR, HS, RB, CRC and JMN. All authors have read
742 and agreed to the published version of the manuscript.
743 Funding
744 French National Research Agency (ANR), Ecole Nationale Supérieure des Mines de Saint-
745 Etienne, Lafarge Division Plaster, OCP group, Technology Agency of the Czech Republic
746 (TA CR) (Grant Number: TH79020003) and German Federal Ministry of Education and
747 Research (Project Number: 033RU020A) support for this project is offered under the
748 coordination of the ERA-MIN3 action, which has received funding from the European Union
749 under the Horizon 2020 Program (European Commission Grant Agreement No. 101003575).
750 Besides, this work also received support by the Federal Ministry of Education, Science and
751 Research (BMBWF) through Austria's Agency for Education and Internationalization
752 (OeAD) [Grant Number: Africa UniNet P006 and P058 as well as WTZ CZ 14/2022 and HR
753 09/2022].
754 Competing Interests
755 The authors have no relevant financial or non-financial interests to disclose.
756 Availability of Data and Materials
757 Data used is openly accessible or can be made available on request.
758 References

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Declaration of Interest Statement

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: