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Abstract Introduction
Large-scale bauxite residue (BR) reuse is still a challenge
for alumina producers worldwide. Agronomic applica- The Bayer process used in the refining of alumina from
tions for BR can be a sustainable and economically viable bauxite ore generates a solid, highly alkaline saline-sodic
option for soil fertility improvement in countries where by-product, referred as bauxite residue (BR), with a global
agriculture plays a crucial economic role, such as Brazil. estimated annual production of 150 million tons (Mt) and a
This study reports a biological approach to partial BR total global inventory estimated at 4.6 billion tons to date
alkalinity neutralization, allowing its safe application as a [1]. The BR is currently disposed of in large purpose-built
soil conditioner for fertility improvement in acidic Bauxite Residue Disposal Areas (BRDA) and new tech-
tropical soils. Microcosm tests were established to assess nologies, such as dry disposal, have been applied to mini-
the effect of incorporating local agro-industrial organic mize land area use [1]. Adoption of technological
residues into the BR to generate acidity, while highly innovations to reduce remaining sodium hydroxide (NaOH)
fertile undisturbed soil was added as a microbial inocu- and water content (press filter) are helping BRDA rehabili-
lum. BR amendment with organic residues exhibited a tation and facilitating BR utilization.
fast pH neutralisation (from 10 to 6.5 at the second day of The International Aluminium Institute (IAI) [2] estab-
incubation). Results confirmed that the locally available lished, at the Alumina Technology Roadmap, a goal to uti-
organic residues and the soil added to BR improved its lize 20% of BR by 2025, but currently, only 2–3% of BR
physical and chemical characteristics, allowing further produced annually is re-used [3]. Consequently, great effort
research into its agronomic effects. has been directed at developing viable applications for the
utilization of BR, aiming to transform it from a waste to a
Keywords valuable product and a secondary source of raw materials,
Bauxite residue Sustainability Soil amelioration generating revenue, decreasing storage areas (and costs
Green mining Zero waste involved) in the process. Unfortunately, of all the BR uti-
lization technologies developed until now, none has resulted
in significant commercial scale application [3, 4]. Currently,
the most promising areas for which BR has large scale
potential utilization comprise construction, chemical, met-
allurgical, environmental and agronomic applications.
Within those, agronomic applications represent a sus-
tainable, environmentally beneficial and potentially
economically viable approach [3, 4], particularly, when
R. B. Holanda P. M. P. Silva A. L. V. do Carmo A. F. Cardoso considering the high demand for fertilizers and soil condi-
R. V. da Costa C. C. A. de Melo A. R. Lucheta (&) tioners in countries that are commodity exporters, such as
SENAI Innovation Institute for Mineral Technology, Av. Com
Brás de Águiar, 548, Bélem, PA 66035-405, Brazil Brazil. Agronomic applications of BR aims to address sev-
e-mail: adriano.isi@senaipa.org.br eral soil issues such as acidity, low water holding capacity
M. Montini and phosphorus losses [4]. Incorporation of BR to degraded
Hydro Alunorte S.A, Rodovia PA-481 km 12, Distrito de acidic sandy soil at 5% (m/v) significantly increased pH,
Murucupe, Barcarena, PA 68447-000, Brazil improved soil texture and water holding capacity, and had
e-mail: marcelo.montini@hydro.com
no significant detrimental effect on the tested plants and composition of BR compared to untreated BR. Outcomes
microorganisms [5]. Although, trials using raw BR as soil from this study will allow further development of a
ameliorant have obtained positive results [5], remediation of BR-based soil conditioner formulations for the improvement
BR prior to use may allow a more effective and safer of fertility in acidic tropical soils.
application [6]. Rehabilitation strategies considered the
organic and/or inorganic amendments to change the BR’s
properties, and thus mitigating critical BR characteristics by Materials and Methods
decreasing pH to < 9, salinity, sodicity, electrical conduc-
tivity (EC) to < 4 mS cm−1 and exchangeable sodium per- Microcosms Experiment
centage (ESP) [7–9].
Bioremediation strategies often aim to add beneficial The BR sample from an industrial alumina refining plant,
properties to BR, transforming it into a soil-like material by located at Pará State, Northern Brazil, was collected in 50 L
improving particle aggregation and nutrient content (organic plastic containers direct after press-filter processing step,
C, NH4+, NO3−, PO43− and K+). Microbial communities under non-sterile conditions, storage at room temperature
play a crucial role in bioremediation, and represent an and shipped to the SENAI Innovation Institute for Mineral
important strategy for lowering BR reuse costs. Local Technologies (ISI-TM), in Belém, Brazil, where the study
microbial communities adapted to the conditions of the BR was conducted.
environment and able to metabolise a range of organic car- Microcosm experiments were carried out to evaluate
bon substrates, including substrates containing a more in situ pH neutralization of BR mixed with organic waste
recalcitrant carbon source such as cellulose and lignin-rich materials, used as carbon sources for microbial metaboliza-
wastes from agro-industry (abundant in countries like Brazil) tion, and soil (microbial inoculum). Residues from a local
and available to nearby alumina plants, are an effective way Palm Oil processing plant: palm mesocarp fiber (PMF),
of providing these microbial input. Complete microbial empty (palm) fruit bunches (EFB), palm oil decanter cake
metabolization of organic substrates generates CO2, that (PODC); Palm Oil refinery: spent Fuller’s earth (SFE) from
under alkaline conditions reacts with hydroxide ion (OH−) palm oil bleaching process; and spent seeds from Açaí
generating bicarbonate (Eq. 1), that also will react with OH− (Euterpe oleracea) beverage processing facility (Fig. 1a)
producing carbonate (Eq. 2). Therefore, carbonation reac- were selected for this study. Organic residues (except for
tions consume two OH− for each CO2 generated. Moreover, PODC and SFE) were dried at 55 °C for 24 h and then
incomplete microbial decomposition of organic material ground in an industrial blender prior to use, to guarantee a
generates organic acids. Together, organic acids generation uniform mixing with BR and soil. Fertile undisturbed soil
and carbonation are the potential mechanisms promoting pH collected from an area hosting native vegetation (classified
acidification of BR amended with organic substrates and/or as Tropical Lowland Ombrophilous Dense Forest), 400 km
soil [4, 9]. northwest of Belém, was added to the microcosm as a
microbial inoculant.
OH þ CO2 ! HCO3 ð1Þ
The microcosm’s setup was based on a modified version
OH þ HCO3 ! CO3 2 þ H2 O ð2Þ of those described by Santini and Peng [11]. It consisted of 5
treatments (one treatment for each organic residue) and 5
Laboratory trials have shown that microbial fermentation controls (3 negative and 2 positives) and were prepared in
of organic substrates dramatically reduce the BR’s pH from 150 mL polyethylene capped bottles (Fig. 1b). The treat-
11 to 7 after few days incubation [8, 10–12]. Considering ments were performed in triplicate and are described in
that raw BR has a much less diverse microbial community Table 1. All tests received 10 g of untreated BR and 100 mL
and lower biomass compared to soil, bioaugmentation of solution (H2O or nutrient medium). The water used was
techniques (addition of a microbial inoculum) have been treated by reverse osmosis, pH adjusted to 10 with 2 M
observed to promote more consistent and rapid BR biore- KOH and sterilized. The nutrient medium, sterilized prior to
mediation [10, 11]. use, had the following composition: 0.15% (w/v) yeast
This study investigated the effect of locally available extract and 0.12% (w/v) peptone, pH 10 (adjusted with 2 M
agro-industrial organic residues and native fertile soil addi- KOH). The pH of organic residues and soil, measured in
tion to the BR as carbon sources and microbial inoculum, H2O (treated by reverse osmosis) at a ratio of 1:5, were: soil
respectively, by assessing changes in its physical and pH 4.4, PODC pH 4.7, SFE pH 3.6, PMF pH 6.5, EFB pH
chemical properties. Microcosms tests containing different 6.9 and Açaí seeds pH 5.8.
organic waste materials and soil were established in the Treatments (T1–T5) consisted of 10 g BR, 15 g organic
laboratory to evaluate their effects on the rates of pH neu- residue, 5 g soil and 100 mL H2O. To CN1 were added 10 g
tralisation and changes in mineralogical and chemical of BR and 100 mL of H2O. Both controls CN2 and CN3
Bayer Process Towards the Circular Economy—Soil Conditioners … 109
Fig. 1 a Organic residues used in the microcosm tests. PMF, EFB and Açaí seeds were dried and ground prior use. PODC and SFE were “in
natura”. b Tests at time zero
Biomass Growth
variations in pH during this period). Positive controls (with Mineralogical composition of the microcosm treatments is
sucrose) exhibited low rates of pH reduction (CP1 pH shown in Fig. 3. Untreated BR, negative (CN1, CN2 and
9.0 ± 2.1 and CP2 7.8 ± 1.7), while no pH neutralisation CN3) and positive (CP1 and CP2) controls and treatments
was obtained in negative controls, as expected. Inversely, the T1, T2, T3 and T5 were predominantly composed of quartz
pH of CN1 and CN2 increased from *pH 10 to pH 12 and (Qz), hematite (Hem), sodalite (Sdl), anatase (Ant), alumi-
pH 11, respectively, during the first days of incubation, nous goethite (Al-Gth), gibbsite (Gbs) and calcite (Cal). The
while the increase in pH observed in the CN3 ceased by latter was not detected in CP2, T1, T2, T3 and T5. Figure 3d
the fourth day. Negative controls pH decreased gradually in shows the mineralogical composition of the residue SFE
the following days, returning to baseline levels on the 28th before microcosm amendment and in treatment T4.
day. While SFE composition was characterized by chlorite (Chl),
Treatments (with organic residues) had faster rates of pH illite (Ill), kaolinite (Kln), palygorskite (Plg) and quartz (Qz),
neutralization than CP1 and CP2 (as well as lower devia- the mineralogy of treatment 4 comprised a combination of
tion), where pH decreased to values between 6 and 8 on the minerals present in both SFE and BR, except for calcite that
2nd day of incubation, remaining in this range until com- was not detected in this treatment. Quartz was the main
pletion of experiments. However, the final pH values of mineral phase found in the soil sample.
Bayer Process Towards the Circular Economy—Soil Conditioners … 111
Fig. 3 Comparison of X-Ray diffraction patterns of microcosm and T4. Qz quartz, Hem hematite, Sdl sodalite, Ant anatase, Al-Gth
treatments and raw materials (BR, soil, SFE). a Unamended BR, soil, aluminous goethite, Gbs gibbsite, Cal calcite, Chl chlorite, Ill illite, Kln
CN1, CN2 and CN3; b unamended BR, soil, CP1 and CP2; kaolinite and Plg palygorskite
c unamended BR, T1, T2, T3 and T5; d unamended BR, soil, SFE
The chemical composition of all microcosm tests indi- 14.94% (T1) to 19.01% (CP2)) and increased Si with values
cated iron (Fe), silicon (Si) and aluminum (Al) as the main between 31.24% (CP2) to 39.72% (T3).
elements (Table 3). Untreated BR contained 36.75% of Fe, Except for CN1 that exhibited similar values to una-
15.55% of Si and 20.09% of Al. While Fe, Al and Si con- mended BR, sodium (Na) and calcium (Ca) content
tents of CN1 remained close to those of BR (36.07, 20.75 decreased in all tests, of which T3 exhibited the lowest Ca
and 15.97%, respectively), the other tests exhibited a content (0.56%) and T1 the lowest Na content (0.86%). The
decreased in the Fe content (values ranging from 16.08% loss on ignition (LOI) measured for untreated BR, negative
(T4) to 28.91% (CP2)), a decreased in the Al (values from and positive controls and T5 ranged from 7.3 to 9.3%, while
112
T3 and T5 were slightly higher (11.9–10.8%). However, for Positive effects of wheat straw, poultry manure compost
T1, T2 and T4, LOI values were greater (15.77, 15.73 and and biosolids additions to BR were reported by Dong et al.
24.84%, respectively), in particular the latter that showed the [16]. Soil (at 5%) was incorporated into BR, and the organic
highest LOI. material was mixed to BR + soil at three different rates: 3, 5
and 10%. The mixture was adjusted to 70% of water holding
capacity, placed in 2 L plastic pots and incubated for one
Discussion year at room temperature (25–30 °C). BR + soil was chosen
as control treatment. BR bulk density decreased and the
The addition of organic residues to BR was effective in concentration of large aggregates increased, in all treatment
reducing the pH and maintaining levels throughout the and addition rates. At the highest rates (10%) of organic
28 days of experiment. No statistically significant differences material addition, compared with the control, all treatments
in final pH were determined when comparing treatments had a decrease in Na content (from 4% to 1.3–1.5%, in
receiving organic wastes with the controls containing the weight), pH (from 11 to *8) and electrical conductivity
disaccharide sucrose (CP1 and CP2), confirming the efficacy (from 1 to *0.3 mS cm−1). Microbial biomass increased in
of these wastes in promoting microbial fermentation of all treatments, but a lower extent than reference soil.
organic carbon. The lowest pH value (pH 6.6) obtained after Treatments’ enzymatic activity (invertase and catalase)
28 days of microcosm incubation was observed in the treat- reached the levels of reference soils, after one year of
ments T1 and T3 (containing PMF and EFB, respectively). treatment. The amount of organic amendment used signifi-
The treatment T4 (with SFE) was the least efficient, with a cantly improved the parameters measured, while no signifi-
final pH of 7.9. Spent fuller’s earth is a sulfuric acid-treated cant differences in values were obtained with the different
bentonite used for carotenoid removal during refining of organic material used. Treatments were effective in
vegetable oils [14], and was the most acidic of the evaluated improving microbial activity, and consequently the authors
residues (pH 3.6). The less pronounced pH neutralization emphasized the importance of establishing microbial eco-
observed in T4 reflects the pH buffering capacity of SFE, that logical functions in rehabilitation practices for sustainable
is superior to the other organic residues, exhibiting smaller ecosystems.
pH value deviations during the experiment. Treatment with Incorporation of organic residues and soil affected the
PMF reached the lowest pH value (5.86 ± 0.07) of all mineralogical and chemical composition of the microcosm
treatments after the 7th day of incubation, however increased tests when compared with unamended BR. The SFE
on subsequent days, possibly due to sodalite dissolution, amendment conferred to treatment T4 distinct mineralogical
buffering the pH in the range of pH 6–8 [15]. profile due its unique composition which possibly resulted in
Previous studies applying organic residues to the BR the marked differences exhibited in parameters such as,
achieved reduction in the pH in a similar timeframe as that in higher pH buffering capacity and greater LOI in comparison
the present study. Microcosm experiments conducted by with the other treatments. The increase in Si content of
Santini and Peng [11] evaluated BR leachate pH neutral- controls and treatments, occurred due to the high content of
ization using distinct organic carbon sources (glucose, Si in the soil (79.74%). Sodium content of the tests showed a
banana, eucalyptus and wood chips), which were compared positive correlation with pH values measured on the com-
with controls containing “BR + soil” or only BR (in solution pletion of incubation period, in which treatments exhibited
with H2O). All tested carbon sources reduced the BR’s pH, considerably lower content in comparison with BR and
with banana and glucose showing the best results (reaching controls.
pH 7.2 and pH 7.4, respectively), while wood chips had the The rapid pH neutralization and marked decreased in Na
lowest reduction (pH 9.0). The pH of “BR + soil” and only content (from 10.3% to 2.2%) obtained in the treatments
BR did not decrease, similarly to CN1 and CN2 that (T1–T5) are major improvements in the BR’s undesirable
remained >10. Tests containing banana showed considerable properties. These traits tend to inhibit plant growth, in par-
reduction pH (from *10 to 7.5) in four days, while in this ticular the salinity stress, impairing the effectiveness of a
study microcosms amended with PMF and EFB had pH 6.9 BR-based soil conditioner.
and 6.7, respectively, in the second day. Santini and Peng The native soil used as microbial inoculum provided
[11] concluded that the extent of pH neutralization is microorganisms able to adapt to the BR characteristics and
determined by labile carbon content, which dictates the rates to metabolise cellulose and lignin-containing substrates (e.g.
of microbial substrate metabolization. Differences in the pH PMF, EFB and Açaí seeds), indicated by pH neutralization
neutralization observed in CN3, CP1 and CP2 confirmed the and the high biomass content of all treatments during the
positive correlation between organic carbon concentration course of the experiment. Future research will focus in
and the acidification of pH. developing a synthetic inoculum based on the isolation of
114 R. B. Holanda et al.