Environmental Nanotechnology, Monitoring & Management 14 (2020) 100322

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Environmental Nanotechnology, Monitoring

& Management
journal homepage: www.elsevier.com/locate/enmm

Is acid treatment of secondary aluminum waste products prior to storage and T

disposal a viable option?
Fatin Samaraa,*, Nour Attiaa, Mustafa Khamisa, Mohamed Hassan Alib, Isra Alama
a
Department of Biology, Chemistry and Environmental Sciences, College of Arts and Sciences, American University of Sharjah, Sharjah, United Arab Emirates
b
Department of Mechanical Engineering, Khalifa University of Science and Technology, Masdar City Campus, Abu Dhabi, United Arab Emirates

A R T I C LE I N FO A B S T R A C T

Keywords: Aluminum (Al) is a widely produced metal in the United Arab Emirates (UAE) particularly for the use in de-
Aluminum Dross velopment and construction industries. The waste products of the aluminum industry are categorized as ha-
Salt Cakes zardous and generally enter municipal waste landfills in the form of aluminum dross and salt cakes. Hence,
metal leachates aluminum industries in the UAE are currently searching for alternative uses and disposal methods for these waste
United Arab Emirates
derivatives. This paper investigates the plausible impacts of the aluminum waste products such as dross and salt
landfills
hazardous waste production
cakes, through material characterization and leaching studies at different reaction conditions. The salt cake and
dross from UAE were characterized by Fourier transformation infrared spectroscopy (FTIR), cation exchange
capacity (CEC) and scanning electron microscopy coupled with energy dispersive X-ray Spectroscopy
(SEM–EDS). The CEC values for salt cake and dross were 425.8 and 408.8 meqH+/100 g sample, respectively.
The FTIR spectra for both wastes showed clear bands for Al (OH)3 and organic functional groups. A treatment
with acidic, neutral and basic aqueous solutions was performed to both waste products and the results showed
that the acid leachate is accompanied with gas evolution and heavy metals, including high concentrations of Al.
The findings of this study prove that aluminum dross and salt cakes could have hazardous implications not only
in the landfill but also in the surrounding environments. A feasible treatment method using acid is suggested in
light of the experimental results to reduce the negative implications of the landfill process while keeping up with
guidelines and goals regarding environmental waste management of aluminum waste products in the UAE.

1. Introduction 1997). Environmentally, aluminum production has been classified as

Aluminum is a light metal of heavy demand both for commercial
and industrial use, and it is projected to increase in demand to 97
million tons by 2020 (Tsakiridis, 2012). Aluminum is extracted from
mined bauxite ore using alumina refining by the Bayer process, fol-
lowed by aluminum smelting by the Hall-Heroult process (Norgate et al.
(2007)). Dross is the waste product of the smelting process from the
primary aluminum and it mainly consists of aluminum, magnesium and
calcium oxides (Al2O3, MgO, CaO) and low concentrations of silicon
and iron (Peterson & Newton, 2002; Li et al., 2014). Primary aluminum
production, with dross as the waste product, has a significant impact on
the environment due to generation of perfluorocarbons gases such CF4
and C2 F6, which are known for their powerful greenhouse gas potential.
In addition, secondary aluminum production results in a waste product
called salt cake (Tsakiridis, 2012).
Presently, dross and salt cake are economically beneficial because
they still retain a significant amount of aluminum (Graczyk et al.,
one of the two light metals with the greatest environmental impacts,
when considering their life cycle assessment from extraction to disposal
(Norgate et al. (2007)). The secondary recovery process is considered to
be gentler on the environment as it only requires 5% of the energy
required during the primary production and releases 95% less green-
house gases (Tsakiridis, 2012). Both, dross and salt cakes are classified
as toxic and hazardous waste due to the high concentration of toxic
metal ions; flammability, and irritant qualities with detrimental effects
on human skin and organs, as well as their high tendency to leach its
contents into water (Peterson (2016)).
Previous studies have shown that salt cakes contain aluminum, ni-
tride, carbide, sulfide and phosphide ions which can react with water or
air to produce harmful gases such as phosphine, hydrogen sulfide,
ammonia gas, sulfur dioxide and methane (Attia et al., 2018). In order
to reduce the effects of salt cakes in the environment, many processes
have been developed to recycle it (Xiao et al., 2005; Li et al., 2012) or
convert it into nonmetal products (Lucheva et al., 2005). One

⁎
Corresponding author.
E-mail address: fsamara@aus.edu (F. Samara).

https://doi.org/10.1016/j.enmm.2020.100322
Received 13 January 2020; Received in revised form 8 May 2020; Accepted 2 June 2020
2215-1532/ © 2020 Elsevier B.V. All rights reserved.
F. Samara, et al.
prominent way of treating the salt cakes waste is a leaching method,
which involves using carbon dioxide saturated water. This method
decreases the transition metal compounds, aluminum phosphide and
calcium fluoride to very low concentrations. The resulting solution can
also be recycled and used as ammonium carbonate fertilizer (Li et al.,
2013). This method has an additional environmental benefit that results
in sequestering the abundant and harmful carbon dioxide by fixing it as
useful fertilizer, thus lowering its environmental impact as greenhouse
gas. Furthermore, other studies have reported on the creation of con-
trolled landfills for the disposal of these hazardous wastes (Gil, 2005,
2007) and generation of high pure hydrogen by hydrolysis in tap water
of highly activated aluminum dross (David & Kopac, 2012).
Recovery techniques such as halite (NaCl) and sylvite (KCl), in ad-
dition to hydrogen gas by treating powdered salt cakes with cold water,
have been suggested to extract useful salts. Metallic compounds in salt
cake waste can be recovered by four methods: flotation, electrostatic
separation, screening and extraction by water (Bruckard & Woodcock,
2009). The last process leads to the generation of hydrogen gas ac-
cording to equation (1), thus providing a new source of green energy
(Bruckard & Woodcock, 2007).
2Al + 6H2 O → 2Al (OH )3 + 3H2 (1)
The Aluminum industries in the UAE, are investing in finding al-
ternative uses for their residues and waste products, hence the aim of
this study was to characterize the secondary aluminum waste products
such as dross and salt cake and conduct leaching experiments to assess
the leaching capacity of heavy metals under different pH conditions.
Through this, the study aims to understand disposal solutions for these
waste products in an attempt to understand how these metals could be
removed in a feasible manner, while keeping in line with the United
Arab Emirates’ vision for future waste management practices.
2. Materials and Methods
2.1. Materials
Salt cakes and dross waste samples were obtained from a local
Aluminum extracting industry in the UAE. All chemicals were of re-
agent grade. Distilled deionized water was used in preparing all solu-
tions.
2.2. Characterization and Leaching Experimentation
2.2.1. Cation Exchange Capacity (CEC)
The base sites were obtained by taking approximately 5.00 g of
dried dross/salt cake samples. 50 meq of calcium acetate were added to
the sample and stirred for 5 minutes, followed by gravity filtration,
rinsing with 50 meq of calcium acetate and an additional filtration. A
second rinse was performed using 20 mL of deionized water and di-
luted. 25.00 mL of the solution was titrated with standardized NaOH
solution. To obtain the cation exchange capacity (CEC); 5.00 g of dried
dross/salt cake samples were weighed and 25 mL of 1 N HCl was added
to the sample and stirred for 10 minutes, followed by gravity filtration,
rinsing with 1 N HCl and an additional filtration. The filtrate was then
discarded and ions exchanged using 100 meq of calcium acetate, fol-
lowed by 20 ml of deionized water and finally titrated with standar-
dized NaOH.
2.2.2. Leaching Experiments in acidic, alkaline and neutral media
Approximately 2.0 g of dried dross/salt cake were added to 100 ml
of three solutions of nitric acid (1%), sodium hydroxide (0.1 M) and
deionized water in duplicates. The solutions were left to stir in a con-
trolled environment of 50 °C to imitate the environment of a landfill
[15]. On the seventh day, all parameters including pH, conductivity and
aliquots for heavy metal analysis were measured for the remaining
solutions. pH was measured using Orion 210A + Basic pH (Thermo
2
Environmental Nanotechnology, Monitoring & Management 14 (2020) 100322
Electron Corporation, U.S), electrical conductivity was measured with
Orion 115A + Basic Cond/TDS/Salinity (Thermo Electron Corporation,
U.S). The pH and EC were measured right after adding salt cake and
dross samples to the solution and after seven days.
2.2.3. FTIR Fourier-Transform Infrared Spectroscopy (FTIR)
Approximately 0.002 g of dried sample was added to 0.2 g of po-
tassium bromide. The mixture was crushed and mixed together using a
mortar and pestle to create a homogeneous sample and then was placed
under 4000 psi pressure to form a disk. Analysis was performed Perkin
ElmerInternational Crystal Lab).
2.2.4. Microwave assisted digestion (MAD) and Sequential Inductively
Coupled Plasma-Optical Emission Spectroscopy (ICP)
Approximately 0.200 g of the dross and salt cake samples were di-
gested with 8 ml of 50% concentrated nitric acid. The digestion was
performed using a Multiwave 3000 SOLV (Anton Paar, Australia). The
microwave program was set to increase the power to 600 W in
10 minutes, held for an additional 10 minutes and finally decreased to
0 W in 40 minutes. The digestion temperature was set to be 180 °C on
the software. The solution was then filtered through a 0.45 μm filter,
then analyzed using ICP.
Seventeen heavy metals were analyzed using Inductively Coupled
Plasma Optical Emission Spectroscopy (ICP-OES) (Varion-liberty,
Australia) using the ICP Expert software including; Aluminum (Al),
Barium (Ba), Cadmium (Cd), Cobalt (Co), Chromium (Cr), Copper (Cu),
Iron (Fe), Manganese (Mn), Nickel (Ni), Lead (Pb), Zinc (Zn), Boron (B),
Selenium (Se), Thallium (Tl), Beryllium (Be), Arsenic (As) and
Vanadium (V). All standards were purchased from Sigma Aldrich.
Calibration standards in the range of 0.01–5 ppm were prepared with
1 M nitric acid for quantification. Blank samples and Quality Control
Standards were also included for quality control purposes, with all
standards rerun at the end of the analysis.
3. Results and Discussion
3.1. Characterization of the raw aluminum secondary waste products
The secondary waste products of aluminum; dross and salt cake
generated from local aluminum industries were characterized in this
study. These waste products are generally known to contain aluminum
which can be recycled and recovered in the aluminum production
process; however, whenever recycling is not feasible, these products are
stored and disposed, in landfill facilities. The risk associated with the
disposal of dross and salt cake in the groundwater environment,
through the formation of landfill leachate, can be assessed by quanti-
fying the leachates such as heavy metal concentrations.
Characterization at different pH levels was conducted to understand the
waste product reactivity under natural environmental conditions, par-
ticularly the conditions present during the normal disposal routes.
The pure aluminum dross and salt cake samples were first char-
acterized as raw materials using FTIR to qualitatively determine any
potential for organic compound formations, and to assess the main
carbon groups within the pure samples. Fig. 1, displays the FTIR spectra
of raw salt cake, raw dross, salt cake after seven days acid treatment
and dross after seven days acid treatment. Inspection of Fig. 1, reveals
that the following peaks occur in raw salt cake: 3863, 3744, 3450,
2935, 2933, 2900, 2354, 1641, 1409,923, 684 and 638 cm-1. On the
other hand, the FTIR spectra of raw dross showed the presence of the
following peaks: 3990, 3801, 3518, 3460, 2926, 2909, 1649, 1490,
1000, 588-780 cm-1.
Upon comparison of these results with the FTIR spectra obtained for
Gibbsite (Al(OH)3), the peaks assigned to stretching frequency of the
OH groups attached to Al are in the range of 3617-3380 cm-1
(Schroeder, 2002). Whereas the bending and out of plane bending vi-
bration occurs at: 500-650, 914, 972, 1021 and 1060 cm-1 (Schroeder,
F. Samara, et al. Environmental Nanotechnology, Monitoring & Management 14 (2020) 100322

3.2. Leaching study of the aluminum secondary waste products

3.2.1. pH and EC
The leaching of dross and salt cake at different pH conditions, which
included acidic, basic and neutral media, was evaluated. The pH and
electrical conductivity of solutions containing salt cake and dross in
water, nitric acid and sodium hydroxide were determined immediately
after initial contact and after seven days contact time, as shown in
Fig. 2. The results of this measurements show that both salt cakes and
dross are alkaline in nature and thus increase the pH of the solution.
The alkalinity of the leachate from salt cake in groundwater from
landfills is a major concern due to its direct and indirect effects on the
surrounding environment and ecosystem. Huang’s et al. (2014), re-
ported similar results when studying several salt cake samples were the
Fig. 1. FTIR spectra of (a) raw salt cake, (b) raw dross, (c) salt cake after seven measured pH was higher than 9.5 when in contact with any media.
days acid treatment and (d) dross after seven days acid treatment. Electrical conductivity (EC) of the dross and salt cakes waste pro-
ducts in acidic, neutral and basic media were also studied. The results
obtained showed that EC increased in the neutral solutions whereas it
2002). Accordingly, all the peaks in raw salt cake and raw dross can be
decreased in acidic and basic solutions (Fig. 3). In the acidic salt cake
safely assigned to Al-OH stretching and bending frequencies, except for
solution, the EC decreased by 70% while in the dross solution it de-
the peaks at 2935, 2933, 2900, 2354, 1641 and 1409 cm-1. These peaks
creased by 85%. In the basic salt cake solution, the EC decreased by
could be attributed C-H stretching frequency (29335-2900) and other
36% while in the dross it decreased by approximately 96%. These re-
functional groups that could be found in these wastes. Hence, FTIR
sults indicate that in the basic medium the leached cations, including
spectroscopy of both raw salt cake and dross samples indicate the
Al3+, react with sodium hydroxide to produce the insoluble hydroxides,
presence of aluminum hydroxide along with other organically active
thus resulting in the observed decrease in electrical conductivity. A
groups. Upon treating both waste products with nitric acid, both dross
decrease of electrical conductivity in the acidic medium indicates the
and salt cake showed a clear change in the spectra at 1409 cm-1 and in
presence of high concentrations of strong conjugate bases of weak
the range of 588-780 cm-1 band. This change could be attributed to both
acids. These strong conjugated bases accept protons from the solution,
oxidation of organic compounds as well as the distortion of the bending
resulting in the decrease in EC values.
frequencies of Al-OH group in the material.
The cation exchange capacity of the aluminum dross and salt cake
3.2.2. Heavy Metals Concentration
products was also assessed in order to understand the strength of the
The presence of selected heavy metals in the dross and salt cake
waste products to bind to the cations present in the sample. Both the
samples was investigated to understand the possible leachability of
dross and the salt cake mimic a texture similar to that of soil, thereby an
those metals under landfill conditions, in comparison to the digested
assumption of the leachability of heavy metal ions in the waste products
raw salt cake and dross. The concentrations of metals obtained from the
was comparable to that of soil. Table 1, shows that both the dross and
digested raw salt cake and digested raw dross, leachates in water; HNO3
salt cake samples had a CEC above 400 meq H+ /100 g of dross/salt
and NaOH using ICP are shown in Table 2. As expected, the aluminum
cake implying that the samples are highly organic. The higher the CEC
concentration in both dross and salt cake was much higher than any
the more likely the rate of exchange of the cations in the material with
other metal present in the samples. When digested, the aluminum
the anions in the surrounding ground. The percent of hydrogen (%HS)
concentration in raw dross and salt cake was 8.98 × 105 mg/kg and
and base saturation (%BS) refers to the number of sites occupied by
3.98 × 105 mg/kg, respectively. Dross is the primary production pro-
hydrogen ions in comparison with the other cations. In both the raw salt
duct; hence, it is expected to have a higher concentration of Al than salt
cake and raw dross samples, the majority of the sites are occupied by
cake, which is the secondary product. On the other hand, as compared
hydrogen ions, at a rate of 90% or higher compared to other cations.
to the digested dross, the digested salt cake had higher concentrations
Therefore, both dross and salt cakes have the ability to exchange hy-
of all metals tested, except for aluminum, copper, vanadium, arsenic,
drogen ions with the anions in the solution. Several studies have shown
cobalt, barium and cadmium.
that when considering the CEC, it is observed that the amount of ex-
The percent removal of aluminum in the acidic medium leachate for
changeable aluminum ions changes with changes in pH. According to
both the dross and salt cake was the highest reaching 60%, as shown in
Duquette & Hendershot (1987), the exchangeable aluminum ions
Table 3. These results confirm that treating both salt cakes and dross
maximize with decreased pH. CEC and pH have a direct proportionality,
with acid prior to discarding in a landfill will extract the majority of
therefore the more basic the material is the more exchange will likely
these metals, thus preventing any contamination to the groundwater
occur. According to the Department of Primary Industries n.d (2020), if
due to leaching. The high percent removal in the leachate of the acidic
a material has low CEC and a high concentration of sodium present, the
media correlates with the high % hydrogen saturation obtained in the
cations will be free in the water surrounding that material; therefore,
CEC experiments, described previously. This happens because the
the cations will be more susceptible to leaching. The aluminum waste
protons in nitric acid are exchanged with the metal cations in the salt
products have a high sodium concentration, which increases the pos-
cake and the dross samples. The exception of this pattern was observed
sibility of the leaching out of cations. By understanding the exchange
for vanadium ions, as no vanadium was leached in the acidic media, but
capacity of the waste products, an estimate of their reaction in natural
34-60% was leached in basic media in both salt cake and dross. The
environments can also be made.
behavior observed is expected as vanadium becomes more available at
higher pH (Reijonen et al. (2016)).
Table 1
The results of this study highlight the high potential of treating both
Cation Exchange capacity of the Aluminum secondary waste products
waste samples before landfilling with acidic medium in order to extract
CEC (meq H+ / 100 g of sample) %HS %BS most of the heavy metals from the salt cake and dross, therefore in-
troducing a more environmentally friendly method for a disposal option
Salt Cake 425.8 ± 1.6 90.1 9.9
Dross 404.8 ± 5.7 94.1 5.9 in aluminum industries. A similar technique was previously shown in
other studies, to recycle salt cakes by allowing it to leach in carbon

3
F. Samara, et al. Environmental Nanotechnology, Monitoring & Management 14 (2020) 100322

Fig. 2. Dross (D) and Salt cakes (SC) pH in acidic, neutral and basic media before and after contact experiment at 25℃. The pH of all solutions used before mixing are
shown under neutral columns for comparison.

Fig. 3. Dross and Salt cakes EC in acidic, neutral and basic media before and after contact experiment at 25℃. The EC of all solutions used before mixing are shown
under neutral columns for comparison.

Table 2
ICP analysis of total and extracted metals in mg/Kg of dross (D) and salt cakes (SC) samples using nitric acid, water and sodium hydroxide.
Metal component Concentration of metals in the digested and leachate samples (mg/kg)

Dig- SC SC- HNO3 SC-H2 O SC-NaOH Dig-D D-HNO3 D-H2 O D-NaOH

Al 3.98 × 105 2.57 × 105 2.46 × 103 2.51 × 105 8.98 × 105 5.48 × 105 3.88 × 103 4.45 × 104
Cu 9.62 × 102 1.26 × 102 8.60 × 101 9.47 × 101 1.03 × 103 9.30 × 101 7.34 × 101 7.38 × 101
Tl 1.59 × 104 3.82 × 102 3.68 × 102 2.76 × 102 4.79 × 103 3.98 × 102 3.43 × 102 2.38 × 103
Fe 5.95 × 103 7.49 × 102 6.57 × 101 8.37 × 101 2.86 × 103 7.67 × 102 3.17 × 101 3.99 × 101
Cr 1.04 × 103 8.03 × 101 2.62 × 101 2.61 × 101 4.72 × 102 5.29 × 101 3.21 × 101 1.98 × 101
V 1.51 × 101 B.D. 2.96 × 10° 5.20 × 10° 2.88 × 101 B.D. 4.18 × 10° 1.73 × 101
Mn 2.61 × 103 1.95 × 103 4.54 × 10° 1.82 × 10° 1.41 × 102 5.58 × 101 4.17 × 10° 4.26 × 10°
As 3.76 × 103 1.58 × 102 4.97 × 102 2.56 × 102 4.01 × 103 1.99 × 102 1.69 × 102 5.03 × 102
B 1.87 × 104 2.08 × 103 1.54 × 103 1.61 × 103 1.42 × 104 1.50 × 103 1.21 × 103 1.32 × 103
Co 6.72 × 101 5.35 × 10° 1.24 × 102 3.53 × 10° 9.82 × 101 1.62 × 101 2.59 × 10° 4.61 × 10°
Ba 1.63 × 102 7.99 × 101 7.56 × 10° 1.71 × 10° 1.51 × 103 1.17 × 103 4.56 × 10° 1.68 × 101
Be 1.70 × 101 2.04 × 10° 1.28 × 10° 8.72 × 10-1 1.30 × 101 9.61 × 10-1 2.87 × 10-1 3.25 × 10-1
Cd 2.91 × 101 3.58 × 10° 4.43 × 10° 9.19 × 10-1 3.40 × 101 1.06 × 10° 2.73 × 10° 2.99 × 10°
Ni 7.54 × 102 2.13 × 102 1.20 × 102 6.07 × 101 3.35 × 102 1.38 × 102 1.15 × 102 8.68 × 101
Pb 4.78 × 102 1.20 × 101 4.77 × 101 2.07 × 101 3.17 × 102 3.25 × 10° 7.44 × 101 3.07 × 101
Se 2.45 × 103 3.48 × 102 2.32 × 102 2.81 × 102 1.81 × 103 3.01 × 102 1.54 × 102 1.80 × 102
Zn 1.47 × 103 1.58 × 102 1.04 × 102 1.38 × 102 9.53 × 102 1.38 × 102 8.57 × 101 1.09 × 102

*Total metals were obtained from acid digestions (Dig-SC and ig-D) and extracted metal were obtained from leachate in nitric acid (SC-HNO3 and D-HNO3), water
(SC-H2O and D-H2O) and sodium hydroxide (SC-NaOH and D-NaOH).
(B.D. =Below Detection)

4
F. Samara, et al. Environmental Nanotechnology, Monitoring & Management 14 (2020) 100322

Table 3 pathways to the heavy metals include ingestion, inhalation, and dermal
Percent removal of metals after 7 day contact solution for acid leachate of salt contact. These metals are categorized as systemic toxicants with the
cake (SC-HNO3 ), water leachate of salt cake (SC-H2 O ), base leachate of salt cake ability to induce adverse health effects in humans [Tchounwou et al.,
(SC-NaOH), acid leachate of dross (D-HNO3 ), water leachate dross (D-H2 O ) and 2012]. Some of these effects include; developmental abnormalities,
base leachate of dross (D-NaOH)
cardiovascular diseases, neurologic and neurobehavioral disorders,
Metal Percent Removal (%) various types of cancer, amongst others [Tchounwou et al., 2012].

SC- HNO3 SC-H2 O SC-NaOH D-HNO3 D-H2 O D-NaOH

3.3. Characterization of the treated aluminum secondary waste products
Al 64.58 0.62 63.10 60.99 0.43 4.96
Cu 13.06 8.94 9.84 9.03 7.13 7.17 After treating the dross and salt cake to neutral, acidic and basic
Tl 2.40 2.31 1.73 8.31 7.15 49.64 conditions, dried material was analyzed by EDS to identify the ele-
Fe 12.59 1.10 1.41 26.79 1.11 1.39
mental composition of the final dross and salt cake. This characteriza-
Cr 7.72 2.52 2.51 11.20 6.81 4.20
V 0.00 19.62 34.51 0.00 14.50 60.10
tion was used to assess whether pH-controlled treatment alone would
Mn 74.86 0.17 0.07 39.56 2.96 3.02 allow for the removal or leaching of more environmentally potent
As 4.21 13.24 6.82 4.97 4.21 12.54 elements from these waste products. The results are seen in Fig. 4 a-f.
B 11.17 8.25 8.64 10.55 8.54 9.30 The EDS, results provides a qualitative assessment of the relative
Co 7.96 18.51 5.25 16.50 2.64 4.70
abundance of the elements on the material post treatment. Under
Ba 49.09 4.64 1.05 77.54 0.30 1.11
Be 11.91 7.48 5.09 7.39 2.21 2.50 neutral treatment Figs. 4 (a) and 4 (b), Aluminum has an abundance of
Cd 12.28 15.21 3.15 3.09 7.94 8.71 around 30%, while elements such as manganese, calcium and magne-
Ni 28.21 15.85 8.05 41.06 34.22 25.89 sium are still present in the material at a much lower percentage, with a
Pb 2.51 9.97 4.34 1.02 23.45 9.68 higher abundance of elements found in the salt cake. When dross and
Se 14.24 9.46 11.49 16.64 8.49 9.94
Zn 10.70 7.07 9.37 14.44 9.00 11.41
salt cake after acidic treatment were examined (Figs. 4 (c) and 4 (d)), it
is observed that in both dross and salt cake samples the most abundant
elements are aluminum, silicon, oxygen and magnesium, suggesting the
Table 4 relative concentrations of heavy metals have been removed from the
RCRA hazardous metals compared to digested metals in dross and salt cake material in the form of acidic leaching. The abundance of aluminum is
in average 45% for both samples. In addition, under basic conditions
Heavy Metal Hazardous Waste Code EPA Allowable Limits Dig-SC Dig-D
(mg/L) (mg/L) (mg/L) the EDS results (Figs. 4 (e) and 4 (f)) shows that while aluminum re-
moval was at about 39% and 16% for the salt cake and dross respec-
Arsenic D004 5 30 32 tively, with the retention of heavy metals such as magnesium, calcium,
Barium D005 100 1 12
manganese, sodium and arsenic in both samples. As a result, it is de-
Cadmium D006 1 0.2 0.3
Chromium D007 5 8 4
termined that the neutral and basic treatment do not offer a reliable
Lead D008 5 4 3 alternative for the removal of heavy metals from salt cake and dross
Selenium D010 1 20 14 samples, yet the acidic treatment could provide a potential alternative
as a tertiary recovery treatment.

dioxide saturated water (Li et al., 2012). The results of our study are
comparable to those observed by Huang et al. (2014), where the total
leachable metals from salt cake to deionized water was 0.6% for alu-
minum, 87% potassium, 54% sodium, 11% calcium, and lover than
0.5% for magnesium, arsenic, chromium, copper and lead. Moreover, a
previous study using X-ray Fluorescence (XRF) in the same samples
used for this study, confirms the presence of Barium at 164.5 ppm and
cobalt at 46.39 ppm, which confirms what was obtained in the current
study. On the other hand, Arsenic, lead, boron, selenium and beryllium
were not detected in those experiments, but where detected in this
study as shown in Table 4, accenting the importance of techniques such
as digestion and ICP-OES to enhance the recoveries of heavy metals
(Attia et al., 2018).
To assess the potential for the dross and the salt cake samples to be
categorized as a hazardous waste, we compared the concentrations of
the digested salt cake and dross (in mg/L) to those listed under provi-
sions of the Resource Conservation and Recovery Act (RCRA) estab-
lished by the United States Environmental Protection Agency (USEPA)
(US EPA, O. (n.d.) (2020)). RCRA has included eight heavy metals
(RCRA 8) and each metal has a designated concentration to determine
whether or not the waste type is hazardous. These metals are: arsenic
(5.0 mg/L), barium (100.0 mg/L), cadmium (1.0 mg/L), chromium
(5.0 mg/L), lead (5.0 mg/L), mercury (0.2 mg/L), selenium (1.0 mg/L),
and silver (5.0 mg/L). The concentration of heavy metals in dross and
salt cake (in mg/L) obtained in this study were compared to six of the
RCRA 8 metals and shown in Table 4. The results show that at least 3 of
the concentrations found in the digested samples exceed the EPA al-
lowable limits including arsenic, chromium and selenium.
Furthermore, Table 4 emphasizes on the possible risk associated
with the improper disposal of the aluminum waste products. Exposure
3.4. Treatment and Disposal of Aluminum secondary waste products
The potential of aluminum recovery of secondary waste products
such as dross and salt cake has been previously discussed, due to the
abundance of aluminum and other oxides in these waste products even
after initial recovery processes. Depending on external economic factors
such as the aluminum market price and the cost of recycling and
transportation, more that 20 % of the metal is often recovered
(Tsakiridis et al., 2013). The most common route for aluminum re-
covery is through processing in rotary salt furnace. This method allows
for the addition of a salt flux at high temperatures which leads to metal
recovery. On average, the method is able to recover 20-40% of the
aluminum present in the secondary waste products (Meshram & Singh,
2018). However, the by-product of salt slag and salt cakes produced
through the process is extremely hazardous due to its high concentra-
tion of chlorides and fluorides (Tsakiridis, 2012). Additionally, the
method is energy intensive and generates additional waste that must
have a separate disposal method, thus effecting the overall economics
of the process.
The common route of disposal of this waste is through municipal
solid waste landfills. The main issue with these products is that the high
level of aluminum in the samples tends to react with other municipal
waste constituents, increasing landfill temperatures and leading to
significantly dangerous reactions such as pyrolysis or combustion in the
surrounding areas (Stark and Calder (2010)). The increase in tem-
peratures and the reaction with the municipal solid waste in the landfill
could also result in the formation of hydrogen sulfides, and ammonia,
which is consistent with the findings obtained in this study through
CEC.
An alternate to the previous method is using complex salt free

5
F. Samara, et al.
Fig. 4. EDS of dross treated under (a) neutral (c) acidic (e) basic conditions and salt cake treated under (b) neutral (d) acidic (f) basic conditions.
methods, which use plasma technology to ensure better salt -free op-
eration and better metal recovery. The metal recovery of these pro-
cesses is on average about 70-80% (Meshram & Singh, 2018). The low
salt content of the slag, and the low release of hazardous gases is also
advantageous in terms of reducing environmental impact, that ad-
vocates the use of such advanced methods. Disposal solutions for these
waste products, such as those using plasma technology, have gained
little attention in terms of the waste management aspect. In European
countries, dross and salt cake disposal in landfills is illegal and so the
solutions they have adapted include waste valorization that would
create incentives in the use of recycling technologies that reuse the
dross and salt cakes during the aluminum production (Reynolds &
Olper, 1990). Historically, countries such as the United States are still
commonly transfer the waste to landfills, as the recovery of aluminum is
not considered economically viable. However, they report that the
6
Environmental Nanotechnology, Monitoring & Management 14 (2020) 100322
storage of these products in the landfills is contained through the use of
specialized liners and controlled landfill environments (Pickens, 2000).
However, considering regions with high aluminum production but low
capital to invest in expensive treatment options, and those that lack the
legislation that incentivizes aluminum recycling, metal recovery and
reduced waste, the high energy requirements renders the overall cost of
such technology unfeasible to be properly established.
Similar to the United States, the United Arab Emirates waste dis-
posal from aluminum industries is sent to landfills under the char-
acterization of hazardous solid waste. The Standard of Practice at the
local center for waste management in the UAE reported that aluminum
dross is categorized as hazardous waste which are stored in cells after
the material passes an elutriation test (Tadweer (n.d.) (2020)). While
guidelines are in place, a recent case study conducted in the country
explores the limitations of waste treatment and overall environmental
F. Samara, et al.
management of the aluminum industry in the UAE (Tadweer (n.d.)
(2020)). Recently, one of the largest industrial companies in the UAE
initiated a waste management system for its under-construction Al
Taweelah alumina refinery. This step sheds light to the importance of
properly managing the waste of this type of material (Tadweer (n.d.)
(2020)). On the other hand, previous studies such as Sajwani & Neilson
(2019), have suggested that aluminum industries do not have robust
governance and enforcement systems, indicating a need for better
mechanisms of compliance to existing laws and regulations for proper
environmental management practices. to implement better practices
and strive for better waste and environmental management solutions.
In light of the mission of the United Arab Emirates to transition
towards zero landfill waste through waste incineration and or pre-
treatment, there is an incentive in advancing better waste management
practices. However, until the infrastructure for better practices is in
place, the present study suggests a potential treatment process that
would limit environmental contamination of heavy metals in the
landfill and subsequently on the country’s groundwater and soil-based
environments. An appropriate treatment strategy according to this
study is to have a batch reactor in which dross salt cake waste is treated
with acid. Leaching of secondary aluminum waste products is con-
sidered a viable treatment option and as expressed in this study, acidic
leaching studies had the highest heavy metal removal rate. In the
proposed batch reactor, the energy requirement for the method is low
due to the use of low reaction conditions, in comparison to the more
energy extensive methods discussed previously. Other works have
suggested acidic medium treatment can result in recovery of aluminum
as high as 95%, thereby the method is adaptable to different reaction
conditions (Dash et al., 2008; Amer, 2010).
While aluminum recovery is lower in this study compared to other
works, the leachability of hazardous heavy metals is quite significant,
thus, reducing environmental impacts of metals such as arsenic
leaching out in landfills. The leached solution can then be treated as
industrial wastewater. The treated waste can be then disposed of in a
controlled landfill with minimum environmental hazard.
4. Conclusion
The high demand for aluminum production worldwide generates a
large volume of waste. A majority of the waste is contained in landfills
and can potentially impact the environment. Dross is the primary
production waste, while salt cakes are the secondary production waste
generated from further extraction of aluminum from the dross. The
results of this study showed that both waste products contained high
concentrations of aluminum in the average of 6.48 × 105 mg/kg, as
well as the presence of several other heavy and trace metals such as
copper, vanadium, arsenic, cobalt, barium and cadmium. At least three
of the chemicals obtained during the digestion of dross and salt cake
exceed the hazardous limits set by the EPA including arsenic and
chromium. In order, to reduce the effects of this heavy metals and the
possibility of leaching in the environment this study suggests a pre-
treatment of the waste in acidic medium which can reduce the con-
centration of metals to approximately 60%.
CRediT authorship contribution statement
Fatin Samara: Conceptualization, Methodology, Resources, Writing
- original draft, Supervision, Project administration. Nour Attia:
Investigation, Writing - review & editing, Validation. Mustafa Khamis:
Conceptualization, Resources, Methodology, Supervision, Writing - re-
view & editing. Mohamed Hassan Ali: Methodology, Resources,
Writing - review & editing. Isra Alam: Writing - review & editing,
Validation.
7
Environmental Nanotechnology, Monitoring & Management 14 (2020) 100322
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors of this paper would like to thank the American
University of Sharjah for supporting this research. Special thanks to the
Department of Biology, Chemistry and Environmental Sciences for their
support in completing the tasks of this research and the Center for
Membrane and Advanced Water Technology, Mechanical Engineering
Department at Khalifa University, Masdar Campus for their help ob-
taining samples. Extended acknowledgements to Mr. Nedal Abufarha
and Mr. Ziad Sara for their help during the analysis of the samples.
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