2 L.G. Plata et al.

/ Journal of Cleaner Production 279 (2021) 123668

elements relatively scarce (Fageria and Nascente, 2014; Korchagin indication of the potential utility of these materials as Ca, K, Mg, P,
et al., 2019). and Si fertilizers. The use of two by-products studied here as a
Since the weathering of principal crystalline phases and the multi-nutrients source for crops can be an alternate technology for
development of secondary phases (crystalline and/or amorphous) the efficient administration of their, which could help to reduce the
is always a very slow process under natural conditions, it is soluble fertilizers utilization.
necessary to understand the dynamics of reactions that affect
mineral dissolution rates for sustainable agricultural production 2. Material and methods
(Sverdrup et al., 2019).
Few studies were performed on multi-nutrients release kinetics Each by-product powder with particle sizes below 5.0 mm for
to date to assess andesite and dacite rock by-products for applica- geochemical, mineralogical and particle size characterization
tion as alternative fertilizer in tropical soil. Information from such experiment was used in this work. Vesicular andesite and dacite
study is fundamental for ensuring safe and efficient use of these by- rocks, respectively, were from Esta ^ncia Velha, and Nova Prata, both
products as soil fertilizer. The investigations into the agricultural of Rio Grande do Sul State (Fig. 1).
potential of minerals and rocks as alternative sources of mainly K The since distribution of the by-products studied has great in-
have been oriented by the fertility notion prevailing in agrarian fluence in nutrients release, because the smaller the grain size, the
sciences. Restricting itself to the evaluation of changes in the soil larger the surface area exposed to exogenous conditions (Ramos
chemical attributes or in the productivity of crops. Without et al., 2017). The particle size distribution of by-products powder
considering the factors associated to release kinetic and to the ef- was determined by using sieves of mesh ASTM 4, 7, 10, 20, and 50,
fects of weathering on the alteration of by-product minerals. according to the methodology described for Brazilian norm, NBR-
Among the nutrients that may be supplied by volcanic rock pow- 7181 (ABNT, 1986). Supplementary details could be found by pre-
ders, K has been the most widely studied to determine whether it viously studies (Ramos et al., 2019; Korchagin et al., 2019). The
can become immediately available in soils at rates significant for masses of the different fractions were recovered and calculated as a
crops (Lybrand and Rasmussen, 2014; Skorina and Allanore, 2015; weight percent (wt %).
Ciceri et al., 2019). Including the several analytical procedures of mineralogical
Many mathematical models and equations (first order, Elovich, characterization, X-ray diffraction is the most indicated in deter-
parabolic diffusion, and power function) have been used to describe mining the crystalline phases present in rocks. This is possible
the kinetics of K release from soil (Jalali and Khanlari, 2014; because in crystals, atoms are ordered on crystalline planes sepa-
Rajashekhar Rao, 2015). Numerous works on K release kinetics rated from each other by distances of the same order of magnitude
were carried out with rock dust in dilute salt solutions, low mo- as X-ray wavelengths (Bunaciu et al., 2015). The mineralogical
lecular weight organic acids (citric and oxalic) and cation exchange phases of the unaltered by-products were determined by X-ray
resins (Silva et al., 2013; Meira et al., 2014). These acids were also diffraction (XRD) in a Philips X-ray diffractometer. The samples
used as extractors in the K and Mg release kinetics by Silva (2016), were homogenized and compacted on the sample holder to obtain
and in the evaluation of the solubility of minerals of volcanic rock a uniform surface, according to previous authors (Ramos et al.,
by Ramos et al. (2015). There is concern about the real effectiveness 2019; Korchagin et al., 2019).
of these materials with the low solubility of rock minerals being the The chemical determination of major elements (in % of oxides
major limiting factor. Knowledge of dissolution kinetics is required weight) of the by-product samples was performed by FRX. Quan-
to properly determine the nutrient supply capacity of rocks to soils; titative analysis was performed using the lithium tetraborate fused
optimize its efficiency as a fertilizer to reduce the use of soluble powder sample technique, with calibration curve from rock pat-
fertilizers and develop guidelines for the safe and proper disposal of terns. X-ray fluorescence technique was employed to determine the
by-products, and reduce ecological contamination (Nishanth and chemical composition of the by-products. The results were pre-
Biswas, 2008; Korchagin et al., 2019). sented in the form of oxides. The chemical conformations of the
Previously studies by Ramos et al. (2015, 2017 and 2019), show rocks by-products were compared between the material collected,
results of the chemical and mineralogical properties of the dacite and the sub-fractions were compared with the total chemical
rock, from the same mining company, used in the present study. composition of the studied rock.
Ramos et al. (2015, 2017), performed leaching tests, in laboratory To estimate the liberation of nutrients by the by-products
conditions, to evaluate nutrient release and potentially toxic ele- studied rocks, the andesite and dacite dust samples, with grain
ments by dacite rock powder in different extractor solutions and size less than 2.8 mm, were subjected to short-time (24e96 h) and
different particle sizes. The authors have suggested that the addi- long-time (96e5760 h) leaching investigations. The leaching tests
tion of dacite rock powder to the soil will not cause risks to human are used to evaluate the chemical stability of the materials, which
health or to the environment, because were that very low levels of when in contact with aqueous solutions, allow to verify the degree
potentially toxic elements were made available to extraction so- of release of their constituent elements. These tests can reproduce
lutions. In addition, the authors concluded that the dacite rock in the laboratory the natural phenomena of dragging, dilution and
powder contains macronutrients important to crop such as Ca, K, desorption that occur by the passage of water through a material.
Mg, and P, jointly with micronutrients like Cu and Zn. In Ramos Such trials may represent several years of the natural leaching
et al. (2019) the potential use of dacite rock powder as soil remi- phenomenon (Tiwari et al., 2015). It is noteworthy that the leaching
neralizer was evaluated in black oats and, sequentially maize crops. test suffers interference from parameters such as temperature,
These authors showed ameliorations in soil attributes, like high extraction solution type, solid/solution ratio, number of extractions,
levels of Ca, K and P and low levels of exchangeable Al and Al specific material surface, degree of agitation used in the test, and
saturation. The authors concluded that dacite rock powder presents mainly the pH of the medium (Tiwari et al., 2015). Therefore, the pH
a viable sustainable alternative that could be replace soluble fer- of the extraction solutions was measured in DM-2P Digimed pH-
tilizers adding value to the investigated rock by-product. meter, to verify the relationships between this parameter and the
Therefore, the principal objective of this work was to assess the chemical elements obtainable in the mixtures. The multi-nutrients
potential and rates of multi-nutrients release from andesite and release kinetics experiments of by-products were performed with
dacite rocks in Milli-Q water, 0.1 mol L
1 citric acid and in Milli-Q different extraction techniques shown in Table 1.
water acidified with acetic acid 0.5 mol L
1 and provide an The multi-nutrients release kinetics experiments were