Journal of Material Cycles and Waste Management

https://doi.org/10.1007/s10163-023-01617-8

REVIEW

Effective and innovative procedures to use phosphogypsum waste

in different application domains: review of the environmental,
economic challenges and life cycle assessment
Brahim Bouargane1 · Khaoula Laaboubi1 · Mohamed Ghali Biyoune1 · Bahcine Bakiz2 · Ali Atbir1

Received: 21 February 2022 / Accepted: 5 February 2023

© Springer Nature Japan KK, part of Springer Nature 2023

Abstract
Phosphogypsum (PG) waste is a by-product generated from wet-process phosphoric acid (­ H3PO4) manufacturing during
phosphate rock decomposition. Worldwide, the annual production of PG ranges between 100 and 300 million tons, with
only a few quantities utilized in several application domains (about 15%), the unused PG is usually discharged into the sea
or stocked in large stockpiles with potential serious human and environmental risks. Therefore, in this review article, we
have studied and discussed the possible alternative ways for PG waste recycling and use. Indeed, this waste material could
be considered as a mineral resource of secondary raw materials within the scope of a circular economy. An inclusive bib-
liographic search, dealing with our review’s objectives, was performed according to the two famous-databases: Web of Sci-
ences and Scopus. After different selecting processes, about 153 articles are found. PG is used in several sectors, including
agriculture, as well as in the brick and cement industry, and road construction. Other applications are reported in this study
such as PG conversion to valuable products and rare earths elements (REEs) extraction. In the same context and in the sense
of reducing greenhouse gasses emissions (GHGs), PG is often used as a calcium source for ­CO2 mineral sequestration. In
addition, different methods of treatment and purification, techno-economic, life cycle and environmental assessment of the
PG recycling, and valorization technologies are summarized and reported in this review. Finally, recent technologies used
for extracting REEs from PG were investigated. The main results, conclusions, and recommendations reported here could
considered as a guide for future studies, and also should be of benefit to scientists, chemists and engineers interested in the
utilization/ treatment of PG.

* Brahim Bouargane
[email protected]
1
LGP, Chemical Department, Faculty of Sciences, Ibn Zohr
University, B.P.: 8106, Agadir, Morocco
2
LME, Chemical Department, Faculty of Sciences, Ibn Zohr
University, B.P.: 8106, Agadir, Morocco

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 Journal of Material Cycles and Waste Management

Graphical Abstract

Keywords Phosphogypsum · Waste · Conversion · Purification · Solubility · REEs · Life cycle assessment

Introduction marketable products, such as phosphoric acid H ­ 3PO4 (PA)

and NPK fertilizers [5–8]. Worldwide, the most common
Phosphorous is multivalent non-metal of the nitrogen group process used for ­H3PO4 manufacture is the dihydrate pro-
useful and well-established donor atoms in coordination cess. This process consists of attacking the natural calcium
chemistry [1]. It is one of the 19 elements strictly indispensa- phosphate ore (apatite) with sulfuric acid according to the
ble for the growth and development of living beings whether simplified scheme shown in Fig. 1 [9–11]. It is formed of a
microbial, plant or animal, and the fifth element composing high concentration of PA containing about 26–30% ­P2O5 and
living matter [2]. This element is an essential component of PG waste containing ­CaSO4.2H2O [12]. This wet-process is
nervous tissue, bone and cell protoplasm. No other element operated at a temperature of 70–80 °C [13]. The PG waste
in the periodic table seems to be able to replace phospho- mainly contains gypsum ­CaSO4.2H2O (~ 95%), and numer-
rous in the three processes specific to life [3]: reproduction, ous impurities (~ 5%) that are dependent to a large extent on
energy transfer and respiratory mechanisms. Phosphorous is the quality of phosphate rock (PR) used, its origin and the
a strategic element for life on earth because of its low availa- preparation process followed during the ­H3PO4 manufacture
bility in most environments [4]. Generally, it originates from [14].
phosphate rocks that are chemically treated, while exploit- As shown in Table 1, the worldwide production of this
able phosphate deposits are limited and concentrated in a waste is measured between 100 to 280 Mt/Year [15–17].
few countries. The phosphate rocks, thus extracted from the Only 45 Mt/Year (~ 15%) of the PG is recycled and used in
mining and phosphates production sites, are converted into agriculture, building, and construction materials [18]. This

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Journal of Material Cycles and Waste Management

PG's massive production, inadequate storage, and high toxic-

ity play a fundamental role in soil and water contamination
[28–30]. From a toxicological point of view, an increase in
the concentration of these elements in the marine environ-
ment could disturb this environment as well as its living
beings, without sparing the highest level of the trophic chain,
which is human [31]. This reflects significant and real envi-
ronmental challenges [32] for the manufacturing units of
­H3PO4 worldwide. To address this issue, many researchers
and laboratories have been exploring effective and innova-
tive methods to use PG as a valuable resource for the prepa-
ration of useful compounds. This valorization provides
added value to many existing industries such as fertilizers,
cement and detergents. In addition, many hydrometallurgical
process technologies used for leaching and extracting both
rare earth elements and heavy metals from PG were inves-
tigated. It is very important to treat, purify, and identify the
different applications of PG.
In summary, based on literature researches, this review
Fig. 1  Simplified schema of phosphoric acid manufacturing process attempts to outline different types of PG pretreatments, uses
and chemical transformations. Advantages and disadvan-
tages of these processes are discussed aiming large scale
Table 1  Average of worldwide PG production management and recycling methods of the large amount of
Countries PG production Mt/Year References
PG produced annually. To the best of our knowledge, the
study of PG use in several domains of applications has been
China > 55 [33] presented largely in many review articles [35, 41, 100], how-
Egypt 0.2 [34] ever, there is no detailed report describe and discuss on the
Jordan 3 [35] same time: the use, transformation, environmental, social
Morocco 15 [36] and economic challenges, and life cycle assessment (LCA)
Senegal(a) ~ 280/ stockpiles [37] study related to the PG field. The results of this study pro-
Serbia 0.8 [38] vide a guide and reference for future research in the field of
Spain 120/ stockpiles [23] PG application and treatment.
Syria 0.4 [39]
Tunisia 10 [40]
Ukraine 10 [41]
USA 35 [42] Materials and methods: methodology
Worldwide produc- Estimated at 280 [16, 17] for the literature review
tion
a
­ 3/stockpiles
166 million m The continuous growth of the world population raises the
need for food supply, that leads to a further increase in the
phosphate fertilizer (PF), phosphoric acid (PA) production
low use is particularly due to the existence of undesirable and, consequently, the annual release of large quantities of
contaminants, such as organic matter, metals, and trace ele- PG waste. The method used to carry out this review study
ments like heavy metals and natural radionuclides [19–21]. consists of identifying first of all scientific publications
The unused PG (~ 85%) is often deposited near the fertilizer related to the "phosphogypsum" by using search key as:
plants in vast stockpiles or discharged into the sea, landfills, phosphogypsum. This study was realized according to the
rivers, and ponds [22–26]. As many countries (including two famous-databases: Web of Sciences and Scopus. The
Morocco) have huge production of PG, the discharge of this results from these tow databases were used to construct the
quantities into the sea could be a practical alternative in Fig. 2. In this figure, the results have been represented as
terms of economy. follows:
Relatively high levels of radionuclides and heavy met-
als in PG could have an impact on the environment which – In Fig. 2a: the number of publications related to the key
makes its commercial use impossible [27]. Remarkably, the search “phosphogypsum” as function of the selected

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Fig. 2  “Phosphogypsum” scientific production as function of: scientific databases (a), years (between 1941 and 2022 results from Scopus Data-
base available at: http://​www.​scopus.​com) (b), scientific areas (c) and countries (d)

databases (between 2012 and 2022). In this period This increase in the PG publication is to find friendly
about 3602 publications are found; routes for PG management, purification, and valorization in
– In Fig. 2b: the number of publications related to the different application domains.
key search “phosphogypsum” between 1941 and 2022 In continuation, the literature review procedure is as
for the Scopus database. This figure shows a noticeable follow:
lack of scientific publications in the period of 1941 to
1970, despite the fact that superphosphates industry has (1) Filtration process: an important number of publications
significantly increased since the Second World War. were identified by selecting the different keywords
The first publications related to PG start to appear only related to the review objective such as valorization,
after 1975. After this period, an exponential increase in management, application, waste, characterization, recy-
the number of articles published from 1975 till today, cling, solubility, agriculture, building, environment,
especially from 2000 to 2022 is clearly noticed. pollution, treatment, carbon dioxide, carbonation, life
– In Fig. 2c: the results are given also as function of the cycle assessment, economic challenge.
scientific areas. Globally, a high proportion of scientific (2) Scanning process: after the filtration process, a scan-
publications are common to many scientific areas; ning process was performed basing on the titles and
– In Fig. 2d: finally, the results are given by countries. abstracts of the above selected publications.
It is remarkably that about five countries contribute (3) Papers selection process: as the subject of this work is
to ~ 50% of the scientific production: China, Spain, “Effective and innovative procedures to use phospho-
Poland, Brazil, and India. gypsum waste in different application domains”, we

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Journal of Material Cycles and Waste Management

have favorably and globally used the recently published simple dissolution in chloride solutions [44, 45]. Numer-
articles. This search is resulting in 153 analyzed publi- ous investigations considered the solubility of SG and PG
cations. in aqueous solutions as described in Table 2. The proce-
dure used in these investigations is shown in Fig. 3.
This paper presents also a brief study on the application The study of PG solubility in multicomponent elec-
of Life Cycle Assessment (LCA) methodology, to assess trolyte aqueous solutions is of significant importance
environmental impacts of PG use and management. Gen- in many disciplines in science and engineering. Basing
erally, the application of LCA in this field is not largely in the literature, it can be seen, that PG solubility was
reported. For that, this review attempts to discuss and ana- studied in different aqueous solutions such as: deionized
lyze the most important decisions taken in recent LCA stud- water, sea water, sodium, potassium and ammonium chlo-
ies. We describe here (See Sect. “Techno-economical and ride solutions. The maximum concentrations of sulfate
life cycle assessment”) several LCA methods, by reporting ­(SO42−) that can be extracted from PG are around 1600
their procedures (Software, data-base, indicators, param- and 1900 mg L ­ −1 using respectively deionized and sea
eters, etc.) and giving the final results for each method. water [46]. While, the highest value of solubility (about
2600 mg ­L −1 of ­S O 42−) was obtained in a salt solution
containing 25 g L­ −1 of NaCl [51]. Thus, using water with
Solubility studies of phosphogypsum a high salt content (sea water or treated brine water) has
the advantages of improving PG solubility and exerting
The solubility measurement of PG and synthetic gyp- lesser pressure on water resources [47]. In diluted acidic
sum (SG) is the widely used information to describe the medium (nitric, hydrochloric and sulfuric) the solubility
behavior and the optimal parameters influencing the dis- constant of PG reaches 3.14 × ­10−5 [48]. For this purpose,
solution of this waste in different solutions [43]. It is also the leaching of PG in acidic solutions is of great interest
of particular importance in chloride hydrometallurgy and in order to extract add-value REEs elements. Generally,
numerous conversion processes, such as the manufacture there is a strong correlation between PG solubility and
of sodium, potassium and ammonium sulfate from PG by acid leaching efficiency [49].

Table 2  Investigations related to solubility measurements of PG

Source Reagent ­ −1
Conc. mol L T Solubility g ­L−1 Comments References
(°C)

SGa Acetic acid 0.25 30 13.5b Solubility increases with increasing [51]
Oxalic acid 14.5b acid for a concentration less than
0.25 M and decreases again at higher
Tartaric acid 9b
concentration
Succinic acid 6.5b
SG Nitric acid 0 to ­30c 60 4.5 Variation of gypsum solubility in [52]
nitric acid passes through a maxi-
mum in the range 22–25 wt.% H ­ NO3
SG HCl-CaCl2 mixture 1 10 to 80 1 Parameters investigated are: [53]
HCl concentration up to 5 M, C­ aCl2
concentration up to 2 M and tem-
perature
SG HCl 3 80 47 Parameters investigated are: [45]
HCl 3 25 24 HCl concentration up to 6 M, and KCl
concentration up to 180 g ­L–1
KCl 130d 25 9
SG NaCl 1 70 0.1b High solubility of PG in chloride [50]
solutions basically attributed to ionic
strength effects but temperature
changes have relatively minor effect
PG 25 25 5.3 Optimal concentration is 25 g ­L−1 of [54]
NaCl
PG and NG e Pure water and lime solution Saturated solution 35 2 Solubility of PG is different to that [55]
of NG due to the presence of some
impurities such as heavy metals and
radionuclides
a
Synthetic gypsum, bhere given as ­[SO42−], c(wt%), d(g ­L−1), enatural gypsum

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Fig. 3  PG solubility measurements, where: SG (Synthetic gypsum), M(G)before (Gypsum mass before dissolution), M(G)after (Gypsum mass after
dissolution), Vsolution (Volume of the chloride solution) and ­X2SO4 (corresponding salt)

In order to better understand the impact of the PG stor- solutions [59]. In all cases, there are two essential treatment
age parameters (in stacks or stockpiles), it is necessary to categories of PG: thermal and wet treatment.
study separately the impact of each parameter (e.g., ionic Several studies have been conducted to purify the PG
strength, Temperature, pH, and conductivity) on the PG sta- waste, improve its quality, and enhance its efficiency to
bility and solubility. The most influential parameters are the accommodate it in many industries: the manufacture of com-
ionic strength and pH, while the temperature changes have posite plaster and Portland cement slag for example [60].
relatively less impact [50]. Taher et al. have studied the thermal behavior of Egyptian
PG at different temperatures [61]. The treated Egyptian PG
was found to contain fewer impurities in P ­ 2O5, fluorides,
Treatment and purification of PG waste and organic matter than raw PG. Likewise, El Issiouy et al.
2013 tested the Moroccan PG, recommending an efficient
The most common PG process involves chemical (pyromet- approach to maximize the elimination of undesirable gas-
allurgical/hydrometallurgical), physical, and thermal treat- ses and volatile impurities. The thermally treated PG was
ment for separation and extraction of critical elements such recommended to be used in the production of sulfuric acid
rare earth elements (REEs), heavy metals and radionuclides. [62]. The thermally purified Tunisian PG presents some
The PG treatment methods are very useful in extracting all strong characteristics that encourage and facilitate its use as
relevant impurities and toxic elements in this by-product a replacement for natural gypsum in the plastering industry
[56]. It is possible to use PG in agriculture and clinker [57, [63]. Generally, drying PG at 60 °C removes free water from
58] instead of natural gypsum by applying appropriate pre- the sample without losing structural water in gypsum [23,
treatment such as flotation, calcination, and wash with acidic 64].

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Generally, all PG dehydration studies using differential phosphorous [75]. A mixture of N ­ a2O:Al2O3:SiO2:H2O
thermal and thermogravimetric analysis (DTA-TGA) indi- (zeolite hydrosodalite) was added to PG, to neutralize its
cate the presence of two anhydrite and hemihydrate associ- acidic impurities. This mechanical activation was suggested
ated endothermic peaks. However, the reported values of to stabilize the properties of the PG and improve its strength
the corresponding temperatures are remarkably different as characteristics [76]. The use of Margin (an industrial by-
peaks were obtained at 130–180, 180–215, and 149–169 °C product less polluting than PG) in the treatment of PG has
[62, 65].The dehydration of pure gypsum takes place in also found its place in the new pre-treatment methods. The
several stages. El Issiouy et al., 2013 find peaks relating to purified PG should be able to be used directly in agricultural
gypsum dehydration separately and precisely, 2 endothermic activities because of the presence of water and organic mat-
peaks at 125 °C and 140 °C corresponding to the dehydra- ter only [75].
tion of dihydrated calcium sulfate to hemihydrate (plaster)
and then to anhydrite III, reflecting a change in the crystal
structure (Gypsum: Monoclinic → Anhydrite II: Hexagonal): Applications and environmental risks of PG
  1st peak (endothermic) at 125 °C:
The general recommendations for managing PG indicate its
CaSO.4 2H2 O(s) → CaSO.4 0.5H2 O(s) + 1.5 H2 O(g) (R1) valorization as the main way for minimizing storage costs
2nd peak (endothermic) at 140 °C: and for reducing the negative environmental effects caused
by this waste [77]. In agriculture, natural gypsum has long
CaSO.4 0.5H2 O(s) → CaSO4 (III)(s) + 0.5 H2 O(g) (R2) been used as a fertilizer for many crops. Some authors have
shown that for many crops, PG is as effective as natural
3rd peak (exothermic) between 320 and 450 °C corre- gypsum. However, the quantities to be used are limited
sponds to crystallographic transformation (anhydrite III: by certain standards [78]. This waste is also used as a soil
orthorhombic → anhydrite II: hexagonal): improver, when deficient in calcium and sulfur, but also for
CaSO4 (s)(III) → CaSO4 (s)(II) (R3) sodic soil permutation, which has been amended by replac-
ing excess sodium with calcium on the soil exchange com-
On the other hand, the impurities existing in PG could plexes (due to the high content in some elements such as
be removed by simple techniques such as washing with dis- Ca, P and S existing in PG). For this purpose, PG is used
tilled, tap or seawater [40]. A significant amount of soluble by peanut growers in various countries. Saline soils, once
impurities have been successfully reduced by three to five treated with PG, regain suitable physical and chemical char-
water washes at a liquid /solid ratio (v/w) of 2:1 (ratio of the acteristics [57, 79]. Other advantages of PG utilization in
water volume per g of PG: 2 ml/g) [66–68]. Similar find- this area are listed in Table 3.
ings have been reported by Liu et al., which confirm that The plaster manufacturing industry is one of the most
all undesirable impurities can be considerably eliminated explored avenues for the development of PG. As noted
by a simple washing technique with deionized water for the above, PG can replace natural gypsum in several industries,
possible use of PG in cemented paste backfill (CPB)[69]. but it is necessary to remove soluble impurities (phosphate,
The less extensive cleaning of PG by rinsing with water, or fluoride and organic matter), since the presence of a small
add a little amount of calcium oxide helps to obtain high- amount of these impurities affects the setting time and
quality gypsum for several industries such as agriculture, strength of the plaster. It is known that PG can traditionally
cement and plaster sectors. An efficacy, cheap and useful be used to slow down the hydration of tri-calcium aluminates
treatment method was proposed by Valkov et al. that claims ­(Ca3Al2O6), by temporarily forming a double sulfate of cal-
using ~ 0.5 M sulfuric acid [70], to extract the rare earth ele- cium and aluminum, ettringite ­Ca6Al2(SO4)(OH)12.26H2O.
ments (REE). The purified PG showed negligible concentra- This practice avoids the phenomenon of stiffening. In the
tions of impurities < 0.02 wt. % [71, 72]. Treating PG with plaster industry, there are two manufacturing processes: (1)
a mixture of sulfuric acid, silica or hot ammonium sulfate Route α: the plaster (called plaster α) is obtained from PG
solution is also necessary to reduce the content of P ­ 2O5 and autoclaved in water at a temperature of 128 °C and a pres-
F in the PG samples before application [73]. A recent study sure of 2 bars. (2) Route β: the PG is heated to 190 °C at
revealed that the content of soluble phosphorus and fluorine normal pressure where it transforms into basanite (plaster
in PG can be reduced by adding lime, and flotation [74]. β). This way is used to produce plasters to be mounted [80].
Seawater seems to be most effective in eliminating the The two routes are done according to the following reaction:
traces of cadmium in PG. But, as it salinizes, it can accu-
mulate large quantities of salts in the purified PG mate- CaSO.4 2H2 O (s) → CaSO.4 0.5H2 O (s) + 1.5H2 O (g) (R4)
rial. However, under these circumstances, the prospect of
using it in plaster industries occurs with less cadmium and

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Currently, only Japan considers the recovery of PG for

References
the manufacture of plaster as profitable because the volcanic

[77, 87]
soil is naturally devoid of gypsum. It thus recovers 3 million

[84]

[86]

[88]

[90]
tons of PG per year [79]. However, the treatment of PG has
proven to be too expensive in most circumstances, and most

The use of PG in this sector required special treatments and neu-

PG is enriched by 226Ra, 210Pb, 232Th, REE, Ba and Cd allowing
uptake of these toxic trace elements and heavy metals (some plaster fabrication plants have gradually stopped their pro-
duction. The use of PG in this area faces other environmental
and economic benefits and risks (Table 3). These problems
can, however, be considered differently if (i) there are lim-
ited resources of natural gypsum in the immediate proxim-
ity and (ii) the quality of the PG by-product is suitable in

tralizing methods (high energy demand)

some cases. The PG has also been used in the manufacture
of cemented materials. It is added to clinkers to reduce the
Negative impact on soil organisms

clinkerization temperature, and adjusts the retarder in Port-

Contamination of groundwaters

land cement. Clinker is partially replaced by materials such

as ash, blast furnace slag and fly limestone during the pro-
duction of composite cement (Table 4) [81]. Finally, and as
References Environmental risks

authors point of view, using treated PG in building materials

radioactive) by

PG high acidity

production (cement, bricks, …) can be safe.

Recent procedures for the recovery of REEs

from PG
[82, 83]

It is well-known that PG contains significant amounts of

[85]

[80]
[77]

[89]
[82]

[81]
[91]
[92]

rare earth elements (REEs), especially, radium and other

It improves the hydration rate as well as the mechanical resistance,
by temporarily forming a double sulphate of calcium and surface

radionuclides [88]. In general, these elements may be fur-

Decreasing the soil organic carbon (SOC) and the total nitrogen

Plaster manufacturing industry Slow down the hydration of tri-calcium aluminates ­(Ca3Al2O6),

Reduce the clinkerization temperature (from 1470 to 1200 °C),

ther grouped, based on atomic mass, into-light rare earth

High compression strength compared to the natural gypsum

elements (LREE) and heavy rare earth elements (HREE)

[95]. These elements co-crystalized with PG due to their
Amendment of the soil habitat and retention functions;

aluminates, ettringite ­[Ca6Al2(SO4)(OH)12.26H2O

isomorphs substitution for C ­ a2+ ions [96]. The increas-

Table 3  Main benefits and environmental risks associated with the PG applications

especially at the 90-day hardness of the cement

ing demand, especially for green energy technology, has

enhanced the need to develop processes for extracting REEs
from PG and other mine wastes as REEs secondary sources
Adjusts the retarder in portland cement
Treatment of acidic or metal-rich soils
Reclamation of the saline-sodic soils

[97]. Moreover, PG samples contain an overall amount of

REE in the range of 0.34–0.64% by mass [98, 99]. The
decomposition of phosphates by sulfuric acid causes the
selective separation and concentration of naturally occurring
Ra, U and Th: about 80% of Ra is migrated in PG, replac-
ing calcium in the chemical structure. While about 86% of
uranium and 70% of thorium is found in the phosphoric acid
loss (TNL)

product. Cerium, lanthanum, and neodymium account for

Benefits

80% of the total REE content of phosphate rock [100]. In the

last few decades, effort has been focused towards the REE
extraction and separation from PG, which has various advan-
tages over traditional REE mining. The main advantage is
the absence of costs for exploration, mining, ore handling,
and comminution [101].
Application domains

Several researchers have reviewed various methods used

Cement industry

for REE recovery from PG. Extraction of rare earths from

Agriculture

PG minerals had been realized by using sulfuric, nitric, and

hydrochloric acids, although nitric acid leaching (nitrophos-
phate process) is incredibly beneficial, however ­H2SO4 is

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Table 4  Use of PG in the cement industry

Treatment type Notes and advantages References

Raw PG Compared to the cements elaborated with natural gypsum, the compression strength is similar at [91]
short times but higher at long times
Raw PG PG can be used directly in the production of Ordinary Portland Cement (OPC). It improves the [92]
hydration rate as well as the mechanical resistance, especially at the 90-day hardness of the
cement
Water-washing and neutralization The removal of soluble impurities or at least reduce these impurities from PG by washing and [93]
neutralization at pH 6–7 makes the use of PG as an additive for cement grinding possible. In
the case of high-quality cement, the PG used as a setting regulator is conditioned by the pres-
ence of syncrystallized P
­ 2O5
Treatment with ammonium Purified PG using a 10 to 20% of ammonium hydroxide solution is suitable for use in the cement [90]
hydroxide solution (­ NH4OH) industry (its mechanical properties are almost similar to those of cement produced from natu-
ral gypsum)
Weathered PG The highest 28-day compressive strength was found in the sample with 3 wt.% PG [22]
Lime milk-washing The 90-day strength of the cement prepared with PG is higher than that prepared with natural [94]
gypsum

economical in the extraction process and it is evident that and Fig. 4 summarizes some other REE leaching procedures
­HNO3 leaching doesn't produce PG [102]. Using a sulfuric from the recent published works.
acid solution (15%) to leach pre-treated PG, at 100 °C for As reported in many reviews, the use of organic meth-
2 h with a liquid/solid weight ratio 3:1, allowed obtaining a ods compared to the conventional hydrometallurgical acidic
final leach liquor with a total REEs content of 4309 mg L­ −1. leaching methods for REE recovery from PG could provide
In all cases, pre-treating the PG, by washing with saline some benefits: the largely reduction of acids consummation,
water (25 g ­L−1 of NaCl) and treatment with a carbonated the major reduction in the leaching solutions volumes, and
solution (60 g ­L−1 of ­Na2CO3), allowed the solubilization the possibility of achieving a much higher selectivity for
of water-soluble impurities and the production of a calcite REE recovery [100]. To purify REE elements additional
phase easily attacked in an acid medium [103]. In case of separation and purification methods such as: precipitation,
nitric and phosphoric acid mixture the REEs take the form solvent extraction, ion exchange and solid phase extraction
of ­REEH2PO42+, ­REENO32+, and ­REE3+. are needed. These methods are highly selective and lead to
In addition to acid leaching methods, there are a few obtain extremely high-quality materials [105].
works that used organic solvents as leaching agents. For As conclusion, the recovery of REEs from PG (consid-
example, the experimental results obtained from [104] show ered as secondary source) through hydrometallurgical pro-
that about 70% of 226Ra, 210Pb, 238U and 40 K were success- cesses is becoming a sustainable and viable approach due
fully removed from the PG by applying this method. Table 5 to the low energy consumption, low waste generation, few

Table 5  A summary of application of acidic and organic reagents in the REE leaching and recovery from PG. Modified from [105]
Leaching type Reagent Experimental conditions Recovery effi- References
ciency (%)
Reagent concentra- t T L:S ratio
tion (mol ­L−1) (min) (°C) (mL ­g−1)

Acidic leaching HNO3 1.5 19.8 80 8 57 [106]

HNO3 7.1 60 72 4 58 [96]
HNO3 3 480 25 30 72 [107]
HCl 1.5 19.8 80 8 51 [106]
H2SO4 1.5 19.8 80 8.0 23.0 [106]
H2SO4 0.8 120.0 50 7.0 52.0 [108]
H2SO4 1.6 90.0 60 1.3 50.0 [109]
Organic leaching TBP–TOPO in kerosene 0.7–0.9 120.0 55 1.0 69.8 [104]
­ a2CO3
TBP‐TOPO in N 0.7–0.9 120.0 55 1.0 80.0 [104]

TBP and TOPO are respectively tributyl phosphate and trioctylphosphine oxide

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 Journal of Material Cycles and Waste Management

Fig. 4  REEs leaching tech-

niques

emissions, environmentally friendliness, and economically

feasibility.

PG chemical conversion into valuable

products

The transformation of PG into certain value-added prod-

ucts using hydrometallurgical routes is extremely interesting
for its economic and environmental advantages in general
frameworks of sustainability and waste management poli-
cies. These methods were used to selectively recover the
calcium and sulfate ions. Recently, researchers have focused
on the development of new wet processes for the transforma-
Fig. 5  PG conversion procedure using hydroxide solution
tion of PG. Compared with other techniques, the wet process
is the simplest and cheapest one. The conversion of PG com-
prises three main steps:

– Pre-treatment and identification of the starting sample

(see the pre-treatment methods previously shown in CaSO.4 2H2 O(s) + 2 XOH(aq)
(R5)
Sect. “Applications and environmental risks of PG”5); → Ca(OH)2 (s) + X2 SO4 (aq) + 2H2 O(l)
– Extraction of calcium and sulfates using different aque-
ous solutions (hydroxide, carbonate, chloride, and fluo- • The carbonation process carried out by injecting a
ride): ­CO2 flow in a Portlandite solution (Ca(OH) 2 formed
– Characterization of the final products. in precedent):

Conversion using hydroxide mediums Ca(OH)2 (s) + CO2 (g) → CaCO3 (s) + H2 O(l) (R6)

The alkaline conversion of PG in aqueous hydroxide solu- So there are two aims for this method, the first is the use
tions under ambient pressure and temperature has been stud- of PG as a calcium source for C ­ O2 mineral sequestration
ied by a number of researchers. The procedure consists of in the framework of the mitigation of greenhouse gasses
two essential steps (Fig. 5): emissions, approximatively 30 Mt of C ­ O2 were utilized
in this process [23]. The second is the production of add-
• Alkaline PG dissolution, the chemical reaction of this values materials for direct application in several areas with
first step can be written as follow (­ R5) with X = Na, K or good conversion efficiency and high purity. For a better
­NH4: understanding of the dissolution mechanism of PG in the
hydroxide aqueous solutions, the authors have studied the
evolution of the pH and conductivity during the conversion

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Journal of Material Cycles and Waste Management

Fig. 6  PG conversion mechanism in hydroxide aqueous solution

process. Then they characterized the solid phases to con- Conversion using carbonate mediums
firm the obtaining of the desired products. The reaction
mechanisms proposed can be represented in Fig. 6 [67, The results of fundamental researches were realized in some
110–113]. Looking more specifically at the dissolution fields of industry; corresponding to the conversion of the PG
of PG and the carbonation process, the initial reactions to ­CaCO3 and K ­ 2SO4 or ­Na2SO4 by using carbonate aqueous
involve these two processes: solutions [116], this procedure has many advantages such as
the fact that it is reproducible, ecological and inexpensive.
1. the dissolution of C­ aSO4.2H2O to give C ­ a2+ ions (­ R7), The calcium carbonate is recovered after filtration and dry-
–
and the decrease in ­OH ions that will combine with ing at 100 °C, then the sulfate obtained after evaporation of
­Ca2+ to precipitate as Ca(OH)2 ­(R8) the supernatant liquid. The chemical reactions are given in
2. The dissolution of C ­ O2 into the water to form carbonic the following [117, 118]:
acid, which dissociates to form finally ­CO32– ions ­(R9).
CaSO.4 2H2 O(s) + K2 CO3 (aq)
(R11)
The carbonate species are then able to form via reaction → K2 SO4 (aq) + CaCO3 (s) + 2H2 O(l)
with the divalent cation (­ Ca2+) resultant in the dissolution of
Ca(OH)2 ­(R10) [114, 115]:
CaSO.4 2H2 O(s) + Na2 CO3 (aq)
(R12)
CaSO.4 2H2 O (s) → Ca2+ (aq) + SO2−
4 (aq) + 2H2
O(l) → Na2 SO4 (aq) + CaCO3 (s) + 2H2 O(l)
(R7)
The production of ammonium sulfate has significant
2+ −
Ca (aq) + 2OH (aq) → Ca(OH)2 (R8) applications, especially in agriculture. It is used as a
source of nitrogen and sulfur for plant nutrition. Burnett,
CO2 (g) + H2 O(l) → H2 CO3 (aq) → H+ (aq) + HCO−3 (aq) from the Florida Institute Oceanography, suggests a prac-
tical solution to the PG problem [119]. The authors pro-
→ 2H+ (aq) + CO2−
3 (aq)
pose converting this waste into ammonium sulfate by the
(R9)
process called Merseburg (Ammonia-carbonation) [120,
Ca2+ (aq) + CO2−
3 (aq) → CaCO3 (s) (R10) 121]. Recently, based on this process, a study has been
conducted on the transformation of Egyptian PG into
ammonium sulfate and calcium carbonate. In this case,
the treatment of PG with sulfuric acid is very effective in

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 Journal of Material Cycles and Waste Management

Fig. 7  PG conversion procedure using carbonate solution Fig. 8  PG conversion procedure using chloride solution

removing the impurities associated with PG and which Conversion using fluoride mediums
contaminate the synthesized products. This procedure is
presented in Fig. 7 [56]. The Merseburg process is based CaF2 formation has its place in the global PG transforma-
on the reaction between gypsum and ammonium carbon- tions; this reaction is possible within 30 min [124]. The con-
ate as shown in the following reaction (R13) [122]: version yield is about 96%, more details are listed in Table 6
( ) and Fig. 9.
CaSO.4 2H2 O(s) + NH4 2 CO3 (aq)
( ) (R13)
→ NH4 2 SO4 (aq) + CaCO3 (s) + 2H2 O(l)
Trace and radioelements distribution

The most important step during the PG hydrometallurgi-

cal conversion was the measurement of the concentration
Conversion using chloride mediums of the toxic elements (i.e., trace and radioelements) existing
in PG and their transfer into the synthesized compounds. In
It is also possible to produce some sulfates from PG using this context, several techniques can be used to calculate the
chloride aqueous solution ­( R 14). The presence of some concentration of these elements during the corresponding
additives (like ammonia or isopropanol) has an efficient process:
role to move in the desired direction and to selectively
crystallize the salt formed, for example potassium sulfate • Inductively coupled plasma mass-spectrometry to the
­K2SO4, as shown in the reaction R15 [68]. characterization of the trace elements: Sr, Cd, V, As, Pb,
La, Cr, Cu, Y…[125, 128];
2CaSO.4 2H2 O(s) + 2KCl(aq)
(R14) • Alpha-particle spectrometry to the characterization of the
→ K2 SO.4 CaSO.4 H2 O(s) + CaCl2 (aq) + H2 O(l) radioelements: uranium (235U and 238U), Thorium (228Th,
229Th, 230Th and 232Th) and lead (210Pb) [38, 129, 130];
2CaSO.4 2H2 O(s) + 2KCl(aq) → K2 SO4 (s) + CaCl2 (aq) + 2H2 O(l) • Gamma spectrometry with Ge detectors to the characteri-
(R15) zation of the radioelements: radium (226Ra), and potas-
Several disadvantages intercept the production of sium (40 K) [131].
­K 2SO 4 by this process. The difficulty of separating the
salt from the other salts can be, to some extent, incon- An important number of works have confirmed that PG
venient [123]. For that, many researchers have succeeded is highly rich in toxic elements [132]. And also most of
in converting the filtrate solution of PG, into calcium these elements would be fixed in the final products: port-
carbonate and ammonium sulfate (Fig. 8), by simple treat- landite, and calcite [23]. They were almost incompletely
ment with ammonium carbonate and sulfuric acid [54]. transferred to the sulfate salts. Tables 7 and 8 represent
the concentration and the transfer factor of some toxic ele-
ments during the transformation of PG into thenardite,
portlandite and calcite [23, 64, 125]. The particular benefi-
cial aspect of this process is the preferential accumulation

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Journal of Material Cycles and Waste Management

Table 6  PG’s conversion into valuable compounds

Alkaline solution Formed products Experimental conditions References
a −1
T (°C) T (min) MR VCO2 (L ­min ) S (rpm)

Hydroxide solutions NaOH Na2SO4 and ­CaCO3 25 180 2 1.2 Constant speed [88, 125]
NaOH Na2SO4 and ­CaCO3 25 90 2.1 3 300 [126]
NH4OH (NH4)2SO4 and ­CaCO3 20 to 80 60 120b 6.7 400 [127]
NH4OH (NH4)2SO4 and ­CaCO3 25 90
2.1 3 300 [126]
KOH K2SO4 and ­CaCO3 25 180 2 to 3 0.02 600 [67]
Carbonate solutions Na2CO3 Na2SO4 and ­CaCO3 Ambient 180 1 – Constant speed [117]
Na2CO3 Na2SO4 and ­CaCO3 80 to 100 120 2
– 500 [103]
NH4CO3 (NH4)2SO4 and ­CaCO3 55 240 1.1 – 150 [56]
K2CO3 K2SO4 and ­CaCO3 Ambient 90 1 – – [118]
Li2CO3 Li2SO4.H2O and C­ aCO3 Ambient 90 1 – Constant speed [36]
Chloride solutions NaCl NaHSO4.H2O and C ­ aCO3 25 –
25c – Constant speed [54]
KCl CaCl2 et ­K2SO4 25 45 50d – Constant speed [68]
Fluoride solutions NaF CaF2 et N
­ a2SO4 25 30 to 120 1.5 to 2 – 600 [124]
a
Molar ratio alkaline solution/CaSO4.2H2O
b
120 wt. % of N
­ H3 (c) g/L (d) 50% excess of PG

presents the general application domains of the products

formed from PG.
In summary, the procedures cited in this review repre-
sent an environmental proposal to jointly enable on-land PG
disposal to be achieved in an environmentally sound man-
ner [63, 143]. Besides, the results indicate that the lower
aqueous solubility of PG is the major problem faced with
the elaboration development of new chemical technology to
convert PG to valuable compounds. Based on this literature
review, we recommend that the appropriate selection of solu-
bility enhancement technique should be considered as key
to revolutionizing the industrial valorization of PG waste.

Fig. 9  PG conversion procedure using fluoride solution

Techno‑economical and life cycle
assessment

of the different radionuclides 238U, 226Ra and 210Pb in cal- It is well known that phosphate rock (PR) could be crude or
cite with an important transfer factor (> 90%). Moreover, upgraded as phosphate concentrates that are used for phos-
calcite is much more soluble than PG in acidic media, phoric acid and phosphates fertilizer manufacturing. PR
which favors the recovery of both rare earth elements production and consumption have increased significantly
(REEs) and radioelements. in different world regions, such as United States, China,
Africa, Middle East, and Eastern Europe, and they are driven
Synthesized products applications by phosphate fertilizers supply and demand, especially in
Eastern Europe, the Middle East, and Africa. The largest
In all cases, these methods give high-purity sulfates, car- phosphate rock producers are Yunnan Yuntianhua Co., Ltd
bonates and fluorites. The researchers recommended apply- (China), OCP (Morocco), Mosaic (United States), and Apatit
ing these compounds directly in several domains. Table 9 OAO (Russia) whereas Africa, Eastern Europe, and the Mid-
dle East are the main phosphate rock exporters [144]. These

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 Journal of Material Cycles and Waste Management

Table 7  Average concentrations Elements PG NaOH Ca(OH)2 Na2SO4 CaCO3

of radioelements during the
(a) (b)
preparation of Ca(OH)2, C C C F C F C F
­Na2SO4 and ­CaCO3 from PG
−1
and Soda, Data from previous Radioelements (Bq ­Kg )
work 210
Pb (± 51) 554.0 < 0.2 1104.0 96.7 21.0 3.6 1124.0 104.7
234
Th (± 8) 63.5 < 0.2 118.0 90.0 3.6 < 0.1 114.0 99.5
232
Th(± 1.5) 7.5 < 0.2 16.0 92.5 < 2.2 < 0.1 16.0 100.8
232
Th (± 32) 502.0 < 0.2 946.0 88.1 12.0 2.2 853.0 92.8
226
Ra (± 80) 670.0 < 0.2 1451.0 101.2 < 9.2 < 0.1 1420.0 100.7
238
U (± 6) 68.0 < 0.2 143.0 102.4 1.5 2.1 128.0 91.9
40
K < 18.0 < 15.0 < 20.0 _ < 16.0 _ < 15.0 _
a
Concentration of the radioelement/ Bq.Kg−1
b
Transfer factors is calculated using the following equation: F= (Ci*mi/⅀Cf*mf)*100, with: Ci and Cf are
respectively the concentration of the selected element present in the starting reactant and in the obtained
product. And mi and mf are the reaction mass (calculate from the reaction of conversion and carbonation
with a stoichiometric molar ratio Phosphogypsum/NaOH=2) of each product: PG (1 g), NaOH (0.47 g)
Portlandite (0.49 g), Thenardite (0.94 g) and Calcite (0.50 g)
c
Error average calculated using the formula: Error (±) = [Error (PG) + Error (Portlandite) + Error (Cal-
cite)]/3

Table 8  Average concentrations Elements PG NaOH Ca(OH)2 Na2SO4 CaCO3

of trace elements during the
(a) (b)
preparation of Ca(OH)2,Na2SO4 C C C F C F C F
and ­CaCO3 from PG and Soda,
data from previous work Trace elements (mg ­Kg−1)
Sr (± 32)(c) 435.0 < 0.1 611.0 68.2 115.0 24.8 476.0 96.5
Y (± 10) 79.0 < 0.1 152.0 93.7 < 0.1 < 0.1 130.0 87.8
Cd (± 0.1) 0.7 < 0.1 1.7 118.0 < 0.1 < 0.1 1.7 99.9
V (± 0.3) 4.5 < 0.1 7.0 75.6 < 0.1 < 0.1 6.0 88.2
Cr (± 0.7) 10.8 2.2 25.3 104.2 5.0 39.9 19.1 77.6
Ag (± 0.04) 0.7 0.2 1.4 90.7 0.2 18.3 1.3 92.5
Se (± 0.36) 3.8 < 0.1 7.1 91.4 0.8 18.8 6.7 97.8
Zn (± 1.56) 7.6 1.0 11.6 69.4 3.2 36.4 13.0 115.3
As (± 0.2) 1.9 0.3 3.2 76.2 0.6 27.6 2.9 94.8
La (± 11.8) 35.5 < 0.1 87.7 120.2 0.2 0.5 100.0 117.3
Pb (± 0.53) 4.1 < 0.5 9.7 115.0 < 0.5 < 0.1 10.2 108.7
Cu (± 1.7) 8.9 1.3 11.7 63.1 2.8 29.2 11.1 97.2
a,b,c
are mentioned in Table 7

Table 9  Application domains of the products formed from PG

Formed product Application domains References

Na2SO4 Detergent, paper industry, glass manufacturing, and textile industry [124, 125]
K2SO4 Agriculture [123]
(NH4)2SO4 Fertilizer industry [126]
Ca(OH)2 Mineral carbonation, formation of calcium oxide CaO nanoparticles and Remineralization of the brine water [122, 133–135]
CaCO3 Paint, plastic, paper, cement, food, textiles, rubbers, Adhesives, cosmetic industry, extraction of iron and [136–140]
pharmaceutical engineering
CaF2 Manufacture of gamma, dental care, treatment of optical Fiber and Fluor industry [124, 141, 142]

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Journal of Material Cycles and Waste Management

companies extract, treat, charge and commercialize phos- from PG residue could become economically feasible provided
phate and its derivatives, in particular phosphoric acid and that suitable extraction processes are available. Based on the
fertilizers. However, this sector is mainly associated with a high price of some REEs (Sc, Sm, La and Y) and on the grow-
large quantity of PG (around 300 MT per year). Generally, ing demand of these elements, PG by-product can represent an
the formed PG is commonly stockpiled in open areas or dis- interesting secondary source of REEs.
seminated into aquatic mediums. Life cycle assessment (LCA) is a multi-step system for
Generally, PG use and valorization in different domain of asserting the lifetime environmental impact of a by-product
applications, offers some social/ ecological benefits such as: [146]. The LCA process is normally iterative as the qual-
ity and completeness of information and its plausibility is
• Employment opportunity: PG processing creates employ- constantly being tested. In all cases, using LCA is a useful
ment opportunities for people in the surrounding areas approach for comparing PG waste valorization and manage-
(Direct and indirect jobs); ment methods within the context of Circular Economy (CE).
• Intergenerational social equity; A description of LCA assessment methods that are used in
• Avoided land use: The recycling of PG is expected to the PG valorization and management field is summarized in
reduce approximately 12,000 ­m2 of land used for stock- Table 10 and explained in detail below.
piling of PG, according to [145]. To the best of our knowledge, few studies dealing with
environmental impact and potential applications of PG
In terms of road construction and according to the study waste, by applying the LCA methods, have been published
investigated by Bentaleb et al., it appears that using PG as a [100]. For example, in a recent study the comparison of
supplement to clay can be beneficial to both environment and alternative management methods for PG using compara-
economic benefits [146]. In comparison with the alternative tive LCA calculation was evaluated [149]. The authors used
used Toufna (Pit-run) as road construction material, the use the data base Ecoinvent 2.0 with the assessment method
of PG in this domain has a Net Present Value (NPV) positive Ecoindicator 99 to compute the ecological footprint of four
in less period (i.e. NPV: a value of all future cash flows over alternative PG waste management methods: (1) the use of
the entire life of an investment discounted to the present) and a PG in brick production, (2) as soil amendment, (3) in road
smaller Payback Period (i.e. PP: is utilized to demonstrate the construction and (4) its disposal in a stack. According to this
period required by a business/process to regain its investment). study, the top ranked method is the use of PG waste as a soil
In fact, Morocco is planning investments of around 2.8 billion amendment, with second the use of PG as a subbase in road
euro for the construction of new rural roads up to 2035. So, works and third the use of PG in brick production. Disposal
Morocco's road industry may represent a potential window for of PG waste in stacks, which is the most common manage-
PG utilization and recycling. In the some context and based ment method was ranked as the least preferred one [149].
on a recent economic case study, the PG can be utilized as Using the same LCA approach, up to 30% energy demand
embankment aggregates in a radius of 29 km keeping a lower reduction and 57% ­CO2 release reduction was achieved with
cost compared to conventional materials [147]. As concluded a ternary system binder based on gypsum-cement-pozzolan
by the authors, this manner of doing will lead to various advan- (GCP) binder if PG was used with practically identical per-
tages such as air emission reduction, and finite natural resources formance of mortar material [150]. This method was done
conservation and protection. Recently, Biyoune et al. analyzed by using the LCA program SimaPro 8 software, and by fol-
the cost benefit of the salinity reduction of the rejected brine lowing the ILCD handbook guidelines and International
water using PG. Based on the output-materials-global-cost esti- Organization for Standardization standards (ISO 14044).
mation, the gain ratio (output cost/ input cost) was calculated as According to these authors, natural gypsum (NG) can be
1.66 [122]. In the same context, the gain ratio of the PG conver- preserved by its replacement with PG. To produce 1t of NG
sion process (into N ­ a2SO4 and ­(NH4)2SO4) was calculated as binder about 1.2 t of NG must be excavated, transferred,
3.43 when using NaOH, whereas this value decreased to 2.02 and treated. Therefore, if the production site is located near
due to the price of ­NH4OH [125]. Carbon dioxide sequestration to the PG stockpiles, the delivery distance is much shorter
is also an additional potential economic benefit, as 1 ton of PG and the storge of PG in stocks is avoided. For environmental
can sequester 0.26 tons of ­CO2 by reacting it with Ca(OH)2 safety, such a management and valorization approach seem
obtained from the PG conversion process using NaOH. Export- logical and must be supported. Comparing two alternative
ing the product of ­CO2 mineralization reaction, ­CaCO3, which solutions: (1) landfilling of this waste in large stockpiles,
is in high demand for, several industries such as construction and (2) implementation of REEs recovery technology, Kul-
and paper production, could generate further revenue [148]. czycka et al. evaluate the management of industrial PG
Preliminary studies of the techno-economic feasibility of the waste in the Wizow plant (in Pland) by taking into account
extraction of rare earth elements (REEs) from PG were evalu- both economic and environmental aspects [151]. Accord-
ated by several researchers. In general, the extraction of REEs ing to these authors, the recovery of REEs from PG waste

13
 Journal of Material Cycles and Waste Management

Table 10  LCA approaches for different phosphogypsum’s valorization and management methods
PG’s type of valorization LCA method or software Database Results Refer-
ences

Chemical conversion into paper LCI/ Simapro Ecoinvent 3 emissionThe findings from LCA indicate that the PG [145]
based paper are not environmentally friendly
in some aspects and also not economically
profitable compared with conventional
products;
Construction Industry SimaPro Ecoinvent With the alternative PG-binder up to 30% of [150]
energy can be saved and 57 wt.% of C ­ O2
emissions can be reduced;
SimaPro 7.3.3 CEN TC350 standards It found that transport had a marked effect [152]
on the categories of eutrophication and
noncarcinogenic effects. The greatest impact
was found when gypsum was transported to a
recycling plant at a distance of 50 km
REEs recovery Eco-indicator 99 – The REEs extraction from PG is cost-effective [151]
but requires significant financial investment,
and it is characterized by a relatively high
degree of risk;
Soil amendment Eco-indicator 99 Ecoinvent 2.0 Use of PG waste as soil amendment to correct [149]
calcium levels in agricultural land has a lower
environmental footprint than using NG;

is considered as a cost-effective and economical process. Conclusions and recommendations

But it is characterized by a relatively high degree of risk.
This is due to the volatility of prices of REEs, as well as a The untreated PG generated by several phosphoric acid
novel, not previously tested technology. [145] proposed a production units, not only poses an environmental threat
new LCA calculation methodology for PG transformation because of the impurities it contains, but also constitutes an
into useful products. They apply process engineering prin- economic loss. Thus, it is necessary to find an alternative
ciples for developing symbiotic pathways on the chemical recovery way. PG contains mainly calcium sulfate, which
transformation of PG and to assess the sustainability of these can be easily recovered and therefore, has an interesting eco-
pathways from social, environmental and economic objec- nomic value to exploit. Research might be pursued to find
tives. There are several indicators that affect the PG chemi- the best ways of recovering this waste. The treatment of PG
cal transformation, including in first degree; Global warming could be very advantageous technology because it allows us
potential (GWP), Eutrophication potential (EP) and Solid to eliminate the maximum impurities present in this waste,
Waste Impact (SWI). The effect of other indicators such as especially the soluble impurities such as P­ 2O5 and fluoride.
human toxicity, land use, water body and ecosystem toxicity, For that, we have shed some light on various ways to purify
is negligible [145]. In this study, two life cycle inventories the PG. The alkaline medium is generally considered to be
for the PG conversion into ­CaCO3 and ­Na2SO4 (using NaOH the best solution to dissolve PG waste, it is therefore rec-
and ­Na2CO3 mediums) were investigated. The process that ommended to study the conversion of this waste in a novel
utilizes NaOH has the highest energy demand compared to alkaline solution or in special mixture of alkaline solutions.
that utilizes ­Na2CO3. The formed ­Na2SO4 could be used Based on this literature review, we recommend that the
in a neigh-boring industry for paper fabrication, while the appropriate selection of solubility enhancement techniques
formed ­CaCO3 is largely used in Cementous materials pro- should be deemed to be key to revolutionizing the indus-
duction. Suarez et al. were used life cycle assessment (LCA) trial valorization of PG waste. Also, extracting REEs from
methodology to evaluate the environmental impact of pri- this waste (considered as a secondary source of REEs) by
mary and secondary gypsum (i.e., PG, NG (natural gyp- hydrometallurgical procedures appears to be a sustainable
sum), RG (red mud) and construction and demolition waste approach with cost-effective and environmentally benefits.
(CDG)) production and its application in the production of Finally, this review can be used as a guide and work of refer-
Portland cement. This study demonstrates that the process of ence to compare, study and applying different processes to
burning natural gas in a furnace to dry gypsum has the great- valorize the high amounts of PG produced annually.
est environmental impact on all environmental categories, As described above, the valorization of PG has attracted
except for respiratory inorganics and land occupation, in the the interest of much scientist and engineers in recent dec-
production of NG [152]. ades, giving rise to several technologies to valorize this

13
Journal of Material Cycles and Waste Management

waste. For this purpose, the authors support and recommend 10. Kazragis A (2010) High-temperature decontamination and uti-
pilot-studies of PG application as a soil fertilizer and as addi- lization of phosphogypsum. J Environ Engin and Land Manag
12(4):138–145. https://​doi.​org/​10.​3846/​16486​897.​2004.​96368​
tive in the building materials production (cement, bricks…). 35
Many applications of PG valorize only a few quantities of 11. Kurkinen S, Virolainen S, Sainio T (2021) Recovery of rare earth
this material. The use of PG in road construction is also of elements from phosphogypsum waste in resin-in-leach process
most interest. It represents the most promising method of by eluting with biodegradable complexing agents. Hydromet-
allurgy 201:105569. https://​doi.​org/​10.​1016/j.​hydro​met.​2021.​
valorization and management of PG, where large amounts 105569
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be preliminary studies, and may suffer from technical and phogypse dans la fabrication des briques cuites. Matériaux Sols
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15. Mattila HP, Zevenhoven R (2015) Mineral carbonation of phos-
Conflict of interest The authors declare that they have no competing phogypsum waste for production of useful carbonate and sulfate
interests. salts. Front Energy Res 3:1–8. https://​doi.​org/​10.​3389/​fenrg.​
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