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Sago pith waste ash as a potential raw material for ceramic and geopolymer
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Article  in  Journal of Material Cycles and Waste Management · October 2017


DOI: 10.1007/s10163-017-0672-7

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J Mater Cycles Waste Manag
DOI 10.1007/s10163-017-0672-7

ORIGINAL ARTICLE

Sago pith waste ash as a potential raw material for ceramic


and geopolymer fabrication
Mohamad Rohaidzat bin Mohamed Rashid1,2 · Mustafa Juma A. Mijarsh3 ·
Hazman Seli4 · Megat Azmi Megat Johari5 · Zainal Arifin Ahmad1 

Received: 2 November 2015 / Accepted: 3 October 2017


© Springer Japan KK 2017

Abstract  This study focuses on the potential usage of sago Both CaO and S ­ iO2 are very significant oxides as they can be
pith waste ash (SPWA) obtained from sago pith waste (SPW) used as an alternative binder for the synthesis of geopolymer
calcined from 500 to 1000 °C. SPWA was characterized by products, especially in combination with other ashes such as
TGA/DTA, XRD, XRF, FTIR, and FESEM incorporating fly ash (FA). Geopolymers fabricated from FA partially sub-
with EDX. About 4% of SPWA was generated from each stituted with SPWA showed a 5% increase in compressive
tonne of SPW at 700 °C as the optimum calcination tem- strength. Therefore, the benefits of SPWA are twofold: first,
perature as indicated by thermal analysis. The phases found as a resource of renewable energy generated through the
in SPWA at calcination temperatures of less than 800 °C burning of SPW which can be utilized by related industries,
are quartz, calcite, and magnesite. XRF analysis found that and second, SPWA itself becomes a potential raw material
SPWA was mainly composed of CaO and ­SiO2 with the for the production of ceramic and geopolymer products.
presence of other oxides such as MgO, F ­ e2O3, and A
­ l 2O 3.
Keywords  Sago pith waste · Characterization ·
Calcination temperatures · Geopolymer
* Zainal Arifin Ahmad
srzainal@usm.my
Mohamad Rohaidzat bin Mohamed Rashid
mrohaidzat@sarawak.uitm.edu.my Introduction
Mustafa Juma A. Mijarsh
eng.mustafajuma@gmail.com Sago is a starch extracted from the spongy centre, or pith, of
various tropical palm stems, especially Metroxylon sagu [1].
Hazman Seli
hazmanseli@sarawak.uitm.edu.my It is traditionally cooked and eaten in various forms such as
rolled into balls, mixed with boiling water to form a paste, or
Megat Azmi Megat Johari
cemamj@usm.my as a pancake. It is often produced commercially in the form
of “pearls”. The sago industry is dominated by Indonesia,
1
Structural Materials Niche Area, School of Materials Papua New Guinea, and Malaysia. The collective amount of
and Mineral Resources Engineering, Universiti Sains
sago produced by these three countries is approximately 2.4
Malaysia, 14300 Nibong Tebal, Penang, Malaysia
2
million hectares of total sago palms. Sago palm is also found
Faculty of Civil Engineering, Universiti Teknologi MARA,
in Vietnam, Thailand, and the Philippines where they exist
Samarahan Kampus, 94300 Kota Samarahan, Sarawak,
Malaysia in limited natural stands [2]. In Malaysia, most of the sago
3 forests have been cleared in the recent decades to pave way
Civil Engineering Department, Faculty of Engineering,
Al-Mergeb University, Al‑Khums, Libya for palm oil, but they still exist in Sarawak, a state in North-
4 ern Borneo, especially in Oya-dalat, Mukah, Pusak-Saratok,
Faculty of Computer and Mathematical Sciences,
Universiti Teknologi MARA, Samarahan Kampus, Igan, and Balingan [3]. Currently, most sago factories in
94300 Kota Samarahan, Sarawak, Malaysia Sarawak are built in the riverine areas for ease of transporta-
5
School of Civil Engineering, Universiti Sains Malaysia, tion and waste management. The waste, i.e., sago pith waste
14300, Nibong Tebal, Penang, Malaysia (SPW) is usually discharged into rivers which leads to river

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pollution [4]. The installation of pollution-control devices is (POFA) [21–24]. To date, no reports on the detailed char-
one of the best methods to solve this problem. SPW disposal acterizations of SPWA can be found. Based on the stud-
could cost about 20–50% of the total investment in a large- ies conducted on the ashes generated from other agricul-
scale factory [5]. tural wastes, there is a strong possibility that SPWA can
Several studies have been conducted to resolve the also be used as a new resource of renewable raw material,
problems and to explore any other potential uses of SPW especially for the fabrication of geopolymer products. The
as a new raw material. These include an investigation on quality of SPWA can be improved and its reactivities can
cadmium sorption characteristics of phosphorylated sago be enhanced via systematic calcination or heat treatment
starch-extraction residue [6], SPWs potential as a probe for process. Therefore, the purpose of this investigation is to
metal ion sensing [7], as well as its use as craft paper [8], report the characteristics of SPW and SPWAs treated at vari-
animal feed, compost for mushroom culture, and substrate ous calcination temperatures and, later, the development of
for local microbes for the production of reducing sugars and compressive strength of geopolymer utilizing fly ash (FA)
enzyme [9]. A study by Quek et al. [10] on the usage of SPW partially substituted with SPWA as a new alternative raw
for the sorption of lead and copper is also one of the efforts material for geopolymer products.
that have been done to minimize waste from the sago indus-
try. In addition, a study by Kadirvelu et al. [11] reported that
SPW could be utilized as an alternative low-cost adsorbent. Materials and methods
They found that SPW activated carbon was very effective in
removing Hg(II) from aqueous solutions and industrial efflu- SPW and SPWA
ents. Besides that, Zainab et al. [12] and Thangavelu et al.
[13], studied the use of SPW materials as fire-retardant or The SPW (wet) (Fig. 1a) was collected from a sago starch-
sound-absorbing panels and as renewable sources of energy, extraction factory (River Link Sago Resources Sdn. Bhd.)
such as bioethanol, respectively. in Mukah, Sarawak, Malaysia. It was first sun-dried for
However, a systematic investigation on the utilization of 2 days before oven drying (SPW dry) (Fig. 1b) for 24 h at a
SPWA generated during the conversion of SPW to energy temperature of 105 °C using a Universal Oven, (UFE 800).
by burning is still lacking compared to investigations done The dried SPW was calcined in an electric arc furnace (Gal-
on other agricultural waste materials, such as rice husk ash lenkamp Muffle Furnace 1000) for 1 h with a heating rate
(RHA) [14, 15], sugar cane bagasse ash (SCBA) [16–18], of 10 °C/min to obtain SPWAs at 6 different temperatures
cassava bagasse ash (CBA) [19, 20], and palm oil fuel ash (SPWA500C to SPWA1000C). The samples were allowed to

Fig. 1  Physical appearances of SPW and SPWAs samples at different calcination temperatures; a SPW (wet), b SPW (dry), c SPWA 500 °C, d
SPWA 600 °C, e SPWA 700 °C, f SPWA 800 °C, g SPWA 900 °C, and h SPWA 1000 °C

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cool before being taken out of the oven. The characterization sand uniformly. The alkali activator solution was then gradu-
of SPWAs was initiated by analyzing the yield and physical ally added into the mix and blended for about 7 min [25].
appearances of SPW and SPWAs with respect to the calcina- Additional water was added to the mix simultaneously with
tion temperatures. The quantitative chemical characteristic the alkali activator to increase the workability as well as
analysis of SPWA was accomplished by X-ray fluorescence homogeneity of the mortar. The mortar specimens were cast
(XRF) (Rigaku Rix 3000) followed with lost on ignition in 50 mm cube steel moulds in three layers of equal height
(LOI) of the samples. The mineralogical phases present in and then compacted. The samples were vibrated to remove
the SPWAs were identified by X-ray diffraction (XRD) using entrained air and bubbles. Immediately after vibration, all
Bragg–Brentano Geometry diffractometer with CuKα radia- samples were covered and kept in the oven for hot curing
tion (Bruker D8 Advance). The thermal characteristics of for 24 h at a temperature of 70 °C. The specimens were then
the SPWAs were determined by thermogravimetric and dif- taken out of the oven and kept in ambient condition with
ferential thermal analyses (TG/DTA) using Shimadzu DTG- an average temperature and humidity of 28 °C and 70%,
60H Differential Thermal Gravimetric Analyser. Fourier respectively, until testing day. A compressive strength test
transforms infrared spectroscopy (FTIR) spectra of SPWA was done using ELE Auto Compressive Testing Machine
samples were obtained using Spectrum 1 FTIR Spectrom- at a pace rate of 0.9 kN/s in accordance with ASTM: C109
eter (Perkin Elmer), while particle size distribution analysis [26]. The compressive strength of the specimens was tested
was determined using laser diffraction analyzer (Malvern after 3, 7, 14, and 28 days, respectively.
Masterizer E). The particle morphology of SPWA samples
were qualitatively determined with the aid of field-emission
scanning electron microscope (FESEM) using Zeiss Supra Results and discussion
35VP, incorporating energy-dispersive spectrometer (EDX).
Figure 1 shows the physical appearances of SPW and SPWA
SPWA geopolymer mortar samples. Wet SPW was yellowish in color and transformed
into yellowish brown upon drying. When SPW was con-
SPWA geopolymer mortar (GSPWA) was prepared using a verted to SPWA at their respective calcination temperatures,
mixture of FA supplied by Lafarge Malaysia Berhad (Asso- the color of SPW progressively changed from yellowish
ciated Pan Malaysia Cement Sdn. Bhd.) and SPWA by per- brown to dark grey. These changes are most likely due to
centage (0–40%) as a binder. The alkaline activators used the increase in the amount of ­Fe2O3 together with the calci-
were a combination of sodium hydroxide (NaOH) in pellet nation temperature, which can be seen in the XRF analysis
form at 98% purity and sodium silicate (­ Na2SiO3) in liquid (Table 1). This inference can be made as, besides ­Fe2O3,
form with a specific gravity of 2.13 g/cm3 at 20 °C. This other oxides do not contribute much to the change in color
alkaline solution was prepared by dissolving NaOH pellets of the samples [27].
and ­Na2SiO3 solution in water. The binder-to-activator ratio Table 1 shows the XRF results for both SPW and SPWA
was kept at 0.5 for all the mixes. Clean silica sand with a samples. As the calcination temperatures increase, LOI of
maximum particle size of 1.18 mm sieve, fineness modulus the sample calcined at 1000 °C decreased from 95.35% in
of 2.8, and specific gravity of 2.65 was used as fine aggre- SPW to 0.51% in SPWA. The main oxides present in SPW
gate. The mixture proportions of the geopolymer samples are and SPWAs calcined between 500 and 1000 °C, which were
given in Table 1. The variable studied in this investigation ­SiO2, CaO, MgO, and F ­ e2O3 with small amounts of ­K2O,
is the substitution of FA with SPWA by percentage from ­Na2O, ­Al2O3, ­P2O5, SrO, and C. Due to the decrease in LOI
0% (GFA as a control) to 40% (GSPWA). Dry FA, SPWA, with increasing calcination temperatures, the percentages
and silica sand were mixed in a cake mixer for about 2 min of each oxide also increased; for example, the amount of
at low rates of speed to blend the source materials and the ­SiO2 increased from 21.74% (SPWA 500 °C) to 35.13%

Table 1  Mixture proportions of geopolymer samples


Mix order SPWA:FA SPWA content (g) FA content (g) Fine aggregate (g) Na2SiO3 (g) NAOH (g) Water (g) Additional
water (g)

GFA 0:100 0 826.90 1240.30 295.30 38.20 79.90 62.00


GSPWA10 10:90 82.70 744.20 1240.30 295.30 38.20 79.90 62.00
GSPWA20 20:80 165.40 661.50 1240.30 295.30 38.20 79.90 62.00
GSPWA30 30:70 248.10 578.80 1240.30 295.30 38.20 79.90 62.00
GSPWA40 40:60 330.80 496.10 1240.30 295.30 38.20 79.90 62.00

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(SPWA-1000 °C) and that of CaO from 16.79% (SPWA- and strength of the synthesized geopolymer mortars are
500 °C) to 26.94% (SPWA-1000 °C). However, ­K2O and dependent on the percentage of FA and RHA used [37].
­Na2O responded to calcination temperature differently; Similar findings were also discovered by Dara and Bhogay-
their quantities decreased as the calcination temperature ata [38], and Shalini et al. [39], who found that replacement
increased, most likely because the oxides tend to evaporate of FA with RHA in small amounts as an additive in the pro-
at higher temperatures. The XRF analysis in Table 1 also duction of geopolymer concrete can enhance the concrete’s
indicates that the CaO content of SPWA is higher compared mechanical strength and ductility.
to other waste ashes. For example, palm oil fuel ash (POFA) Figure 2 shows the phase transformation of SPW when
only has < 8% CaO [28, 29], slag mixtures have < 5% CaO calcined from 500 to 1000 °C. SPW is a completely amor-
[30], fly ash has only < 2–4% CaO [31–33], and bottom ash phous phase, and when calcined at 500 °C, phases such
has < 11.4% CaO [34], while red mud and RHA have < 3% as calcite (­ CaCO3, ICDD no. 98-002-3938), quartz (­ SiO2,
CaO [35]. Similarly, the amount of ­SiO2 content in SPWA ICDD no. 98-005-4692), and magnesite (­ MgCO3, ICDD no.
was lower compared to that in other industrial waste ashes 98-006-1859) were observed. These phases steadily reacted
such as FA which has 51.5% S ­ iO2 and 1.74% CaO [28] and with one another to form new phases such as wollastonite
slag that has 34.58% S­ iO2 and 40.67% CaO [36]. Therefore, [Ca(SiO3), ICDD no. 98-001-7684] and fayalite ­[Fe2(SiO4),
the application of SPWA as a raw material for geopolymer ICDD no. 98-002-2754] together with the transformation
synthesis can be done by combining it with other ashes as of ­SiO2 crystals into cristobalite (­ SiO2, ICDD no. 98-006-
a supplementary material. Specifically, SPWA can be com- 1837), especially at the calcination temperature range of
pared to RHA (considered as a reactive source material rich 800–1000 °C. These results also prove that the major com-
in silica) which contains a higher amount of S­ iO2 (91.93%) positions of SPWA at calcination temperatures of less than
[37]. RHA is still successfully used to synthesize geopoly- 800 °C are quartz, calcite, and magnesite, which are in line
mers as it is used to partially replace FA. The workability with the results obtained from XRF analysis (Table 2).

Fig. 2  XRD diffractograms of
SPW and SPWAs calcined from
500 to 1000 °C

Table 2  Composition of SPW, Sample code SiO2 CaO MgO C K2O Na2O Al2O3 P2O5 Fe2O3 SrO LOI
FA, and SPWA (wt%) by XRF
SPW 1.34 0.71 0.25 0.13 0.24 0.32 0.07 0.05 0.77 0.01 95.29
FLY ASH 50.03 5.14 1.40 8.03 1.34 0.21 23.54 1.04 6.44 0.55 2.28
SPWA-500 °C 21.74 16.79 7.65 0.75 6.54 6.98 0.81 1.10 1.80 0.32 21.30
SPWA-600 °C 21.86 17.13 8.84 0.78 5.41 6.14 0.80 1.27 4.89 0.34 18.50
SPWA-700 °C 22.95 18.29 9.27 0.80 3.86 4.70 0.99 1.36 6.06 0.37 17.51
SPWA-800 °C 32.32 24.52 11.12 0.81 2.18 2.44 1.03 1.64 6.80 0.48 7.2
SPWA-900 °C 34.43 25.79 12.72 0.83 1.11 1.87 1.36 2.06 6.91 0.52 3.92
SPWA-1000 °C 35.13 26.94 13.51 1.18 1.04 2.19 1.39 2.14 7.07 0.54 0.51

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Figure  3 shows DTA/TG for SPW and SPWAs Table 3  Yield of SPWA sample at different calcination conditions
(500–1000 °C). As shown in Fig. 3a, SPW experienced Sample Before cal- After calcined (g) % Yield
various changes when calcined up to 1000 °C. The first cined (kg)
change was at the vicinity of 50 °C where SPW started to
SPWA-500 °C 1 56.33 5.63
release moisture and other volatile compounds present in the
SPWA-600 °C 1 55.81 5.58
samples. Moreover, most of the carbonaceous compounds
SPWA-700 °C 1 53.92 5.39
burned between 200 and 400 °C with two exothermic DTA
SPWA-800 °C 1 52.58 5.26
peaks and great weight loss. It can be seen that the SPWA
SPWA-900 °C 1 41.22 4.12
samples became stable as the temperature reached 500 °C.
SPWA-1000 °C 1 39.84 3.98
These results were consistent until calcination temperatures
reached 1000 °C. Figure 3b–g shows the DTA/TG of SPWAs
with different calcination temperatures, which explain the
results of weight loss (by percentage) that are similar to the Figure 4 shows the FTIR spectra for SPW and SPWAs
results of LOI (Table 1). (calcined from 500 to 1000 °C). Four similar bonds exist
The differences of each SPWA sample with respect in both SPW and SPWAs; these include the H–O–H bond
to yield at various calcination temperatures are shown in at 3456  cm−1, O–H stretching at 1646  cm−1, carbonate
Table 3. The yield decreased with increasing calcination group at 1440  cm −1, and Si–O bending between bonds
temperatures and became constant (4%) as the calcination around 1039–1085  cm −1. These bands prove that the
temperatures went beyond 800 °C. Therefore, by simple cal- major compounds in SPW and SPWA are quartz and cal-
culation, the amount of SPWA generated by the calcination cite. Other small bands in SPW such as 2915 cm−1 (C–H
process is around 0.04 tonne for each tonne of SPW. stretch), 1248 cm−1 (C–O–C of carbonate soft segment) and

Fig. 3  TGA/DTA of SPW and SPWA materials under various calcination conditions; a SPW, b SPWA-500  °C, c SPWA-600  °C, d SPWA-
700 °C, e SPWA-800 °C, f SPWA-900 °C, and g SPWA-1000 °C

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Fig. 4  FTIR spectra of SPW and SPWAs materials under calcinations process from 500 to 1000 °C

Table 4  Particle sizes of SPWAs under different burning conditions shape and size. This is due to the formation of phases such
as wollastonite, fayalite, and cristobalite.
Samples Dv10 (μm) Dv50 (μm) Dv90 (μm)
Based on the above analyses, SPWA can be considered as
SPWA-500 °C 5.50 63.8 196 a potential new resource of renewable raw material that can
SPWA-600 °C 6.76 64.3 206 be used in the fabrication of the traditional ceramic prod-
SPWA-700 °C 6.28 42.3 238 ucts. However, in this study, SPWA was specifically tested
SPWA-800 °C 6.65 44.1 181 as partial substitution of FA in geopolymer fabrication up to
SPWA-900 °C 6.28 31.3 149 40 wt%. The compressive strengths at the ages of 3, 7, 14,
SPWA-1000 °C 7.94 45.0 191 and 28 curing days are shown in Fig. 6. There is an obvious
effect on compressive strength when FA was partially sub-
stituted with SPWA. The strength initially increased (10 wt%
599 cm−1 (Si–O–Si) disappeared and produced new small SPWA, GSPWA10) and started to decrease with increasing
peaks at 799 cm−1 (Si–O bending), 713 cm−1 (calcite), and amounts of SPWA. The highest compressive strength (47 N/
between 473 and 481 cm−1 (Si–O–Si) in SPWAs. The peaks mm2) was obtained from GSPWA10 sample at 28 days. This
at 2511, 1803, and 877 cm−1 belong to the carbonate group, is about 5% higher compared to the pure FA geopolymer
mainly for calcite, which was only present in SPWA cal- (control sample). This proves that SPWA is a high reactive
cined from 500 to 800 °C [40–42]. The hydroxyl band at material and is as good as other waste materials such as
3648 cm−1 and the peaks at 678 and 644 cm−1 belonging to RHA, SCWA, SCBA, and POFA.
Si–O stretching can be seen as the calcination temperatures However, as SPWA increased > 20%, the compressive
increased from 800 to 1000 °C [43, 44]. The two peaks at strength of the geopolymer samples started to decrease. This
678 and 644 cm−1 prove the appearances of cristobalite as is due to the decreasing amount of ­Al2O3 originating from
also indicated by XRD analysis (Fig. 2) when SPW was FA, resulting in increased ­SiO2/Al2O3 ratio in the samples
calcined at higher temperatures. (Table 5). Therefore, the increasing ­SiO2/Al2O3 ratio con-
Particle size analyses using laser diffraction analyzer tributes to the decrease in compressive strength, since the
(Malvern Masterizer E) for all SPWA samples are shown amount of mullite (­ Al6Si2O13, ICDD no. 01-083-1881) for-
in Table 4. There is no specific trend for the average par- mation in the geopolymer also decreased. This is proven by
ticle size with respect to calcination temperatures. The the XRD analysis of samples which were cured for 28 days,
results of D v50 for 500  °C are around 63.8 μm and it as shown in Fig. 7. Al(OH)4−4 species in geopolymer samples
showed almost a 50% decrease when calcined at 900 °C. is an important factor for condensation purposes in these
This is related to various transformation states of samples materials as the Al component tends to dissolve easier than
as discussed in XRD, XRF, and FTIR analyses. The par- the silicon components; this enables a higher rate of conden-
ticle size observation can be further visualized from the sation between the silicate and aluminate species compared
FESEM analysis, as shown in Fig. 5, where the SPWAs to the condensation between just silicate species, resulting
reduced in size as the calcination temperature increased. in a higher initial compressive strength [28].
When the temperatures reached or > 900 °C, the parti- In addition, similar findings were made by Chindapra-
cle size increased due to the agglomeration and change in sirt et al. [45] through their study on the effects of alkali

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Fig. 5  SEM images of SPWA materials under calcination temperatures from 500 to 1000 °C

activator and RHA content on the strength of geopolymer


mortar. They found that higher amounts of Si/Al ratios are
associated with lower strength and higher elasticity in geo-
polymers. At a certain level, an increased proportion of RHA
may result in a higher percentage of unreacted or partially
reacted RHA particles in the geopolymer system, making the
final geopolymeric products weaker and less ductile. Duxson
et al. [46] also reported that high Si/Al ratio and low A­ lO4
species in geopolymer formation result in strength reduc-
tion as this condition does not favour condensation of long-
chain polymeric structure; therefore, they act as defect sites
and exert a negative effect on the strength of geopolymeric
materials.
Therefore, this preliminary study indicates that there is
a potential usage of SPWA as a component in the fabrica-
Fig. 6  Compressive strength of the geopolymer samples tion of FA-based geopolymers similar to other agricultural
waste such as RHA, SCBA, CBA, and POFA. However, this
material needs to be further explored, especially for other

Table 5  Chemical composition Sample code SiO2 CaO MgO C K2O Na2O Al2O3 P2O5 Fe2O3 SiO2/Al2O3 LOI
of SPWA-700 °C, FA, GFA,
and GSPWA SPWA-700 °C 22.95 18.29 9.27 0.80 3.86 4.70 0.99 1.36 6.06 – 17.51
FLY ASH 50.03 5.14 1.40 8.03 1.34 0.21 23.54 1.04 6.44 2.13 2.28
GFA 60.13 3.69 0.52 3.34 1.21 3.61 18.63 0.63 3.91 3.23 2.68
GSPWA10 60.33 5.76 0.51 2.36 1.27 3.49 17.77 0.96 4.07 3.40 1.10
GSPWA20 59.39 7.57 0.68 2.42 2.24 3.82 15.24 0.94 3.88 3.90 1.58
GSPWA30 58.40 9.33 0.77 2.59 2.56 3.90 14.08 0.88 3.40 4.15 1.89
GSPWA40 55.80 11.54 0.94 3.61 2.64 4.22 11.82 0.84 3.23 4.72 2.75

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Fig. 7  XRD diffractograms of
raw FA, SPWA 700 °C, GFA,
and GSPWAs samples

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