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Article

Recycling Bio-Based Wastes into Road-Base Binder: Mechanical, Leaching, and Radiological Implications

by
B. Peceño
1,
S. Hurtado-Bermudez
2,
B. Alonso-Fariñas
3,
M. Villa-Alfageme
2,
J. L. Más
4 and
C. Leiva
3,*
1
Escuela de Prevención de Riesgos y Medioambiente, Facultad de Ciencias del Mar, Universidad Católica del Norte, Larrondo 1281, Coquimbo, Chile
2
Dpto. Física Aplicada II, ETSA, Universidad de Sevilla, Avda. Reina Mercedes 2, 41012 Seville, Spain
3
Dpto. Ingeniería Química y Ambiental, ETS-Ingeniería, University of Seville, Camino de los Descubrimientos s/n, Pabellón Plaza de América, 41092 Seville, Spain
4
Dpto. Física Aplicada I, ETSI-Informática, Universidad de Sevilla, Avda. Reina Mercedes s/n, 41012 Seville, Spain
*
Author to whom correspondence should be addressed.
Appl. Sci. 2023, 13(3), 1644; https://doi.org/10.3390/app13031644
Submission received: 21 December 2022 / Revised: 20 January 2023 / Accepted: 25 January 2023 / Published: 27 January 2023
(This article belongs to the Special Issue Recent Development in Utilization of Waste Ash for Construction Materials)
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Abstract

:
This work presents a physical, mechanical, durability, leaching, and radiological assay of three wastes (egg and scallop shells and olive pomace ash) as road-base binders. Two different waste/Portland-cement ratios (7.5/92.5 and 80/20) were studied. Density and compressive strength decreased when different wastes were added in every proportion. Additions of 7.5% of both shells reduce the density to about 2.5% and the compressive strength to 20%, while 80% reduces the density to 20% and the compressive strength to 90%, while the addition of biomass fly ash decreases the density and compressive strength in a higher proportion than shells. The durability against acid attack is increased when the three wastes are used, and this increase is higher when the waste dosage is increased (up to 15 times more when 80% biomass ash is used). With respect to leaching, scallop and eggshells can be used as a component of hydraulic road binder, but olive pomace ash presents leaching values higher than the limits of different regulations (Se, Pb, Ni, Mo, Cu, and As). From a radiological perspective, all road-base binders present an activity concentration index lower than 1, except when olive pomace ash was used, and the binders showed higher values of 40K due to the high potassium content of fly ash.

1. Introduction

A road-base binder is a powder, made of a mix of different components, which is the basis for constructing hydraulically bound base mixtures for the treatment of materials for bases, sub-bases and capping layers, and earthworks in airports, roads, railways, and other infrastructures [1]. Portland cement, bituminous materials, lime, and industrial wastes such as slag, furnace dust, coal fly ash, and others (up to 10% by mass) are the most common materials used in road binders [2]. Although there is potential for the use of waste materials and the reduced consumption of high-value components such as cement [1], there are few investigations related to the incorporation of waste in road binders [2], especially the environmental (heavy metals and radioisotopes) assessment of the waste incorporated. Mainly, the incorporation of waste in hydraulic road binders has focused on wood ash [3], cellulose ash [2], and steel slag [4]. Therefore, at present, the technical and environmental feasibility of incorporating other wastes composed mainly of limestone, such as seashells and eggshells, is unknown. No previous studies have been extended to other types of ash, such as olive pomace ash.
European standards EN 13282-2 [5] on additives to road-base binders indicate the characteristics that certain wastes must have to be used in this kind of application. One of them is that the waste cannot emit radiation or contain hazardous materials. Even so, the standards do not always specify the tests that must be performed or the maximum limits that cannot be exceeded, and that is what this study attempts to investigate in depth. Globally, population growth has caused an increase in the demand for manufactured food and, therefore, an increase in waste generation [6]. On the other hand, worldwide, construction demands more natural resources than any other sector [7]. To improve the environmental sustainability of construction and other sectors, different wastes, some of a biological nature, have been evaluated as substitutes for materials traditionally used in construction (cement, mortar, and concrete) [8].
For example, the global aquaculture industry produces between six and eight million tons per year of seashells from different sources (scallops, oysters, mussels, cockles, etc.) [9]. Approximately 60% of total production becomes waste [10] and only 25% of this is reused [11]. Furthermore, the disposal of seashell waste generates unpleasant odors and requires a large area of land for dumping [12]. The same environmental problems occur in the poultry industry, which generates more than 250,000 tons of eggshell waste per year [13]. Other biological wastes are generated in the agricultural sector, such as olive pomace. It is estimated that a ton of processed olives produces approximately 27% olive oil and 73% waste. In Andalusia (Spain) alone, three million tons/year of pomace are generated [14]. The improper management of olive pomace can cause major environmental problems due to its high phenol content [15].
Eggshells are useful in various construction materials, such as cement [16], mortar, concretes, alkali-activated binders, and bricks [17] (due to their high calcium carbonate content. Eggshell powder has shown good strength parameters when mixed with concrete, from previous studies shown below [18]. There are previous studies on the use of seashell waste in cement production [19], as a fine/coarse aggregate in concrete [20,21,22], and as fireproof materials [11].
Due to its high energy content and low fuel cost, olive pomace is used as biomass; approximately 30% is used to produce electric energy. However, the combustion of olive pomace produces more than 50,000 tons/year of ash [14]. These ashes have been used in cement manufacturing [23], bricks [24], fireproof materials [25], geopolymers [14,26], and mortar [27].
In this study, three different wastes of biological origins (eggshells, seashells from scallops, and ashes from biomass combustion (olive oil pomace)), have been used as raw materials in road binder.
Although these three wastes are biological in origin, previous studies have declared the presence of heavy metals in eggshells [28,29] and seashells [30]. Olive oil pomace ash contains heavy metals (such as As and Pb) and a high content of potassium [25]. Therefore, these wastes could contain leachable heavy metals and radioisotopes, which, although present in low concentrations in the waste, make their use as construction materials unviable due to health and environmental risks.
The research significance of this study is to assess and compare the physical, mechanical, and environmental properties of road binders when part of the cement is replaced by different bio-wastes (fly ash from olive pomace, eggshells, and seashells) into road binders in different proportions.

2. Materials and Methods

2.1. Tested Materials

Portland cement (CP) type II 32.5 N according to European standards [31] was used. The cement particle size was less than 90 µm Three different wastes have been analyzed: (1) Chilean–Peruvian scallop shells (Argopecten purpuritas) (SC) from the Chilean aquaculture industry were used. The material was previously crushed to obtain a particle size lower than 350 μm. (2) Eggshell (E) was generated as solid waste generated from bakeries and was previously crushed to a particle size of less than 350 μm. (3) Fly ash (OR) from olive pomace combustion in a power plant in southern Spain was used. The ash was sieved to obtain a maximum particle size of 350 μm. The particle size distribution is shown in Figure 1. It was measured by using a Saturn DigiSizer II model. Egg and scallop shells present the highest differential percentages between 50 and 250 μm and are similar for all the sizes of this interval, The average particle size of scallop shells is 98 μm, as shown in Figure 1. Eggshells present a medium value (85 μm) slightly lower than scallop shells. Fly ash from olive pomace combustion presents the highest differential percentages in the range between 20 and 150 μm with a medium particle size of 44 µm, but all of them are higher than Portland cement.
The chemical composition of the materials was determined after chemical attack and dissolution at 750 °C (ASTM D 3682 [32]) using atomic absorption spectroscopy. Table 1 shows the main chemical components; the composition is expressed as oxides (but this does not imply that they are present in the material as oxides, either before or after calcination). The specific density was obtained according to ASTM D 854 [33].
As shown in Table 1, the main component in the shells of eggs (E) and scallops (SC) was calcium carbonate [11,12,13]. The calcium carbonate decomposes at a temperature between 650 and 700 °C, so when analyzed after its calcination, CaO appears and the LOI collects, which corresponds to CO2 decomposed during the previous calcination. Additionally, the eggshells presented a little more SiO2, Fe2O3, and SO3. However, the scallop shells presented a greater amount of Na because, unlike eggshells, they are in contact with seawater. Olive oil pomace ash is mainly composed of silica and potassium, and the LOI value is due to the unburned matter present in the ash. According to EN 13282-2 [5], all wastes complied with the permitted concentration of SO3: less than 4%.
The specific gravities of these wastes are lower than those of Portland cement (CP). Both types of shells present a similar specific density because they have a similar chemical composition.

2.2. Specimen Manufacturing Method

Although additives greater than 10% are not recommended according to EN 13282-2 [5], 7.5 and 80% replacements were carried out to obtain significant differences in the radiological study, keeping the water/solid ratio constant and equal to 0.35. The different compositions are shown in Table 2.
Cement and waste were mixed for 4 min until a homogeneous mixture was obtained, for all the different compositions. After adding water to the mixture and mixing for 5 min, a workable mixture was obtained. Cylinder molds were filled once the mixture had reached the proper consistency. After 24 h, the material was demolded, then cured for another 27 days at 20 °C and 60% relative humidity.

2.3. Physical and Mechanical Properties

The density was calculated in accordance with EN 1936 [34]. The compressive strength (CS) of the test specimens was determined based on the EN 196-1 [35] using a compression test machine (Tinus-Olsen). These tests were carried out on 4 × 4 × 4 cm prismatic specimens. Each result was obtained by testing three specimens.

2.4. Durability: Resistance to Acid Attack

In many applications under severe environmental conditions, the choice of a binder influenced the durability of finished materials, and in this work, mechanical resistance under a chemical attack (acid) has been studied.
The resistance to acid attack (RA) of the hydraulic road binder has been measured according to previous studies [36]. After a 28-day curing period, some samples were immersed in water (reference specimens) and others in a 1 M sulfuric acid solution for 14 days. Three samples in water and three in acid have been tested for each composition. The compressive strength of the attacked specimens was measured (CS-acid) and reference specimens (CS-water) were compared according to the equation:
R A = C S − a c i d C S − w a t e r

2.5. Environmental Study

European standards EN 13282-2 [5] indicate the characteristics that some wastes should meet to be used in road-base binders. One of them is that waste should not contain dangerous leaching substances or emit radiation.

2.5.1. Leaching Study

The most common leaching test in Europe is EN-12457-4 [37], and it is used to classify wastes according to the EU Landfill Directive [38]. The test is very simple. For materials with particle size distributions less than 10 mm, it is based on single-stage leaching at a liquid/solid ratio of 10/1. The mixed liquid/solid was rotated for 24 h at 15 rpm. Deionized water was used in this study. An ICP spectrometer (Agilent Technologies, Madrid, Spain) from the Research, Technology, and Innovation Center at the University of Seville (CITIUS) was used. Two leaching tests for each leaching were carried out.
In addition, this test is used in some European national and regional leaching regulations in order to assess the use of waste in construction applications. For instance, Portugal [39], Italy [40], and some regions of Spain (Catalonia [41] and Basque Country [42]) have established leaching limits according to this test’s results for the valorization of wastes as construction materials Metal analysis in leachates have been carried out through the Inductively Coupled Plasma technique.

2.5.2. Radiological Study

Radioactive nuclides are found in varying amounts in traditional building materials and wastes [43]. Natural building materials and wastes contain various amounts of natural radioactive nuclides [43]. Many wastes could be considered NORM (naturally occurring radioactive material) [44], and their use is subject to the legal restrictions of international radiation protection safety standards, such as the European Directive 2013/59 [45]. These standards establish several parameters to characterize the final construction material containing wastes: activity concentration index (I), the absorbed dose (D, Gy/h), radium activity (Raeq), and effective dose (E, Sv/y). All these parameters are obtained by their activity concentration (in Bq/kg) of 232Th and 238U series radionuclides, and 40K, which can be determined by gamma-ray spectrometry [8].
Two samples were tested for each composition. Cylinder specimens were positioned directly at the top of the detector endcap. A Canberra low-background high-purity germanium GR-6022 reverse electrode coaxial (XtRa) detector (60% relative efficiency) shielded by a 10 cm-thick high-purity lead served as the primary detector. The detector was connected to a DSA-1000 digital spectrum analyzer. The spectra were analyzed using Canberra Genie 2000 gamma software (version 3.2). All the samples were related to one day of sampling. The activity concentrations of the different gamma emitters were determined through the energies of 232Th (911.2 keV of 228Ac), 238U (or its daughter 226Ra via 351 keV emissions of 214Pb), and 40K (1460 keV).
Additionally, a Low Energy Germanium (LEGe) GL-2020 detector was used for checking performance at low and moderate energies because it was fabricated with a thin side and front contact affording a better resolution than any other detector. The LEGe detector had an active area of 2000 mm2 and thickness of 20 mm, and a 0.6 mm carbon epoxy window that improves ruggedness while maintaining good low-energy transmission was used.
The detectors’ absolute efficiencies were calculated using Canberra LabSOCS software, which is based on the MCNP Monte Carlo code, considering the self-absorption of low-energy gamma rays within the sample [46]. The minimum detectable activity (MDA) and the decision level of both detectors for 40K, 210Pb, 238U, and 232Th were calculated according to ISO 11929-4 [47]. Additionally, an alternative geometry was checked by placing a cylinder specimen viewed from the side (see Figure 2). The MDA values for this measuring geometry were compared with the geometry of a cylinder specimen viewed from the top.
Finally, the gamma-ray spectrometry analyses were validated based on several inter-comparison programs [46,48].
The gamma radiation dose was calculated to assess the radiological hazard of the proposed hydraulic binders. Activity concentrations of 226Ra, 232Th, and 40K were converted into the absorbed gamma dose rate (D) using the conversion factors presented in the literature [49] at 1 m above ground (in mGy/h by Bq/kg):
D n G h = 0.462 · a R a − 226 + 0.604 · a T h − 232 + 0.147 · a k − 40
Then, D can be converted into the annual effective dose indoors (E) according to Equation (3):
E m S v y = 0.8 · 10 − 6 · Q · D · T
where (1) Q is a converting value of 0.7 Sv/Gy for gamma-ray environmental exposure; (2) the indoor occupancy factor of 0.8 indicates that 80% of the time was spent indoors; and (3) T is the time, equal to 1 year (8760 h.) [49].
On the other hand, the activity concentration index (I) is defined as:
I = a R a − 226 300 + a T h − 232 200 + a K − 40 3000
where ax is the activity concentration of nuclide x in the construction material analyzed (Bq/kg).
According to the European Commission Radiation Protection 112 technical guide [50], it was developed as a tool for screening construction materials.
“I” gives an assessment of the gamma radiation dose that an individual may receive from construction materials. For bulk materials, if I ≤ 1.0; E is ≤1 mSv/y and the material could be used safely from a radiological point of view.
Finally, radium activity (Raeq) determines the radiological hazards of 232Th, 226Ra, and 40K distributed in construction materials. Raeq is a weighted sum of the activity concentrations of the radionuclides considering that 259 Bq/kg of 232Th and 4810 Bq/kg of 40K cause the same gamma dose due to 370 Bq/kg of 226Ra [51].
R a e q = a R a − 226 + ( 1.43 · a T h − 232 + 0.077 · a K − 40 )
where ax is the nuclide x activity concentration (Bq/kg).
A safe construction material produces an external dose below 1.5 mGy/y, corresponding to a Raeq value lower than 370 Bq/kg.
JASP R-based statistical software (version 0.14.1) was used for statistical analysis. Pearson’s correlation was calculated to consider the relationships between the physicochemical properties, radioactivity concentrations, and radiological parameters. Positive correlations are shown in blue, while negative correlations are shown in red on a correlation heat map. Correlations with p-values greater than 0.01 were considered insignificant, correlations with p-values less than 0.05 implied a 5% probability of random chance, p-values less than 0.01 implied a 1% probability, and p-values less than 0.001 implied a 0.1% probability of random chance.

3. Results and Discussion

3.1. Physico-Mechanical Properties of Road-Base Binder

The density and CS of road-base binders decrease when different wastes are added in any dosage, as shown in Table 3. The density was reduced because 1) wastes present a higher particle size distribution than cement, which increases porosity between particles, and 2) wastes have lower specific gravity than cement and, consequently, a higher porosity within the particles (see Table 1). In this study, the specific gravity and particle size distribution of the egg and scallop shells are similar, producing densities very similar. When OR is used, the particle size is lower than both shells, and the specific gravity is like the other two wastes, producing a denser material.
Also, the CS decreased when all wastes were added and when the proportion was increased. From a physical point of view, egg and scallop shells present a similar density, and, therefore, they have similar porosities, but they are higher than only Portland cement binders (CP-100). From a chemical point of view, scallop and eggshells are principally calcium carbonate and, therefore, they are an inactive addition because they do not have pozzolanic properties [52]. Both effects diminish the compressive strength when both wastes are added at a similar level. When OR is added, the compressive strength is reduced more than the shells’ addition due to the low reactivity of this kind of ash and because when OR is added, the compressive strength is reduced more than shells’ addition, due to the low reactivity of OR and because the number of principal hydration outputs of cement such as C-S-H and Ca(OH)2 are diminished [53].
Regardless of the type of waste, the compositions made with 7.5% waste and CP meet the minimum mechanical requirements to be used as normal hardening road-base binders according to EN 13282-2 2. CP-92.5-OR-7.5 and CP-92.5-E-7.5 could be classified as N2 (compressive strength between 12.5 and 32.5 MPa), while CP-92.5-SC-7.5 and CP could be classified as N4 (compressive strength between 32.5 and 52.5 MPa). If the compressive strength is compared with road binder containing waste-paper ash in a similar dosage [54], the compressive strength is higher in the three wastes analyzed in this work, but lower when steel slag is used [55].

3.2. Durability: Acid Resistance of Roa- Base Binders

As shown in Figure 3, when the amount of waste in the binder is increased, the acid attack coefficient increases. For specimens CP-20-OR-80, CP-20-SC-80, and CP-20-E-80, the acid attack coefficient is greater than 1. Part of the Ca present in waste and cement in an acidic environment dissolves in water so that Ca2+ reacts with SO42−, producing CaSO4 ·2H2O. As shown in Figure 4, the acid attack caused the generation of a gypsum layer on the surface and inside the specimen, giving the specimens a white appearance. This formed gypsum has a higher compressive strength than the material before the acid attack [56]), so in cases of high waste dosage, it increases compression resistance. However, in materials with higher initial compressive strength and lower porosity (higher density), the gypsum induces higher volumetric expansions and leads to the spalling of the surface layers, producing a diminution after the attack [57].

3.3. Leaching Results

The construction materials must not pose a hazard to the safety, health, or hygiene, of occupants, neighbors, or workers. Moreover, they must not have a high impact on the environment during their useful life. Although, there are no specific regulations on the emissions of heavy metals in hydraulic road binder-containing wastes in Europe. Italy [39] and Portugal [40] have national regulations and Spain presents some regional regulations (Catalonia [41] and Basque Country [42]) for the recycling of the wastes in construction materials according to the European standard leaching test EN12457-4, the same one the European Union uses to limit the emissions of leaching heavy metals in waste landfills [38]. All use the same test but establish different limits for the same elements.
The European Directive defines three waste categories: hazardous, non-hazardous, and inert wastes. Table 4 compares leaching data from the three wastes and Portland cement to the European Directive limits [38]. Regarding [38], OR can be considered a non-hazardous waste due to its As and Pb content being higher than the inert limit and lower than the non-hazardous limit. Scallop and eggshells can be considered inert wastes. In Portugal, waste recycling is allowed by the Portuguese Environment Agency [39] when limits for the inert waste of [38] are not exceeded in construction materials. Both shells could be reused, but not biomass fly ash.
On the other hand, Italian Ministerial Decree 5 [40] establishes the maximum limits that waste must leach if it wants to be used in construction according to EN12457-4. Regarding the Italian Decree [40], Table 4 shows that OR (and CP) cannot be used in construction materials in Italy due to high values of Se, Pb, Ni, Mo, Cu, and As. Scallop and eggshells meet all the requirements in Italian legislation.
In Spain, there are no established national limits about the leaching emissions of hazardous heavy metals of construction materials containing wastes. However, for example in the case of Spain, there are regional laws that allow, based on the results of EN 12457-4, the establishment of whether waste can be used in specific construction applications (pavements, roads), such as the Autonomous Government of Catalonia and Basque Country. These legislations establish different limits for the same compounds (and are different from the Italian and Portuguese norms). They even establish limits for compounds that are not limited in others (i.e., Hg, Pb, Sb, As, and Cu are limited in Catalonia and not in Basque Country and, V is limited in Basque Country and not in Catalonia). These limits can be observed in previous studies [58]. According to these limits. scallop and eggshells can be used but biomass fly ash exceeds the limits regarding Se, Mo, and Ni in both regulations and Pb, As, and Cu in Catalonia limits.

3.4. Radiological Results

Table 5 shows the activity concentration values of 232Th, 226Ra, and 40K. All specimens showed activity concentrations for 226Ra and 232Th lower than typical concentrations for concrete in the EU [59] (35 Bq/kg for 232Th and 60 Bq/kg for 226Ra), but values above 392 Bq/kg for 40K (EU average) were achieved. Binders containing other wastes (such as titanium dioxide waste [60] or red mud [61]) present higher activity concentrations than OR (of 226Ra and 232Th), sin embargo when co-combustion fly ash is used [62] the activity concentrations are lower than OR but higher than egg and scallop shells. In particular, the behavior of specimens composed of biomass fly ash is noteworthy (CP-20-OR-80 and CP-92.5-OR-7.5).
The component responsible for this radioactivity concentration value, which is an order of magnitude higher than the average, must be the OR incorporated into the material. During the growing process, olive pomace is naturally enriched in potassium (radioactive and stable isotopes) from fertilizers and soil. When olive pomace is used as biofuel, it has a K2O concentration of up to 22.5%, which corresponds to 5200 Bq/kg. When fly ash is added to a road-base binder in an 80%wt ratio, 40K activity concentrations can be estimated to be around 4000 Bq/kg, which corresponds to the CP-20-OR-80 activity.
On the contrary, construction materials containing sea and eggshells did not have either 40K or nuclides from the 238U and 232Th series. Their activity concentrations were the lowest values found in this study, even lower than road-base binders containing only Portland cement. The potassium concentration in the shells was very low (<0.2% in Table 1). The inclusion of these shells dilutes the concentration of natural activity of the cement itself by removing any additional activity.
As shown in Table 6, almost all specimens produced an I index lower than 0.5; those of cement and mixes of cement with seashells and eggshells are three times less than those of OR. This finding suggests the possibility of using these matrices as dilution agents for building materials. CP-92.5-OR-7.5 also produced a dose rate lower than 0.3 mSv/y. However, when the dosage of OR increases to 80% (CP-20-OR-80), the dose rate is higher than 0.3 mSv/y, and its use should be restricted, but it could be used for restricted uses (boards, tiles, etc.) or superficial materials.
Regarding the Raeq of the materials, it can be noticed that no specimens show Raeq higher than 370 Bq/kg (the recommended value). The lowest values were obtained for CP-20-E-80, CP-20-SC-80, CP-92.7-E-7.5, and CP-92.7-SC-7.5.
Finally, except for CP-20-OR-80, most samples forecasted absorbed dose rates and annual effective doses were lower than the global average indoor absorbed dose rate (84 nGy/h) reported in UNSCEAR Annex B [49]. CP-20-OR-80 had values above the limit and should be ruled out for use in building materials. All maximum annual effective doses are below 1mSv/y [48].

3.5. Statistical Results

Pearson’s correlation coefficients (r) were calculated and are shown in Figure 5. A positive correlation was observed between thorium and radium with correlation coefficients of r = 0.933, but not with 40K. The role of potassium is completely independent of the other natural radioactive chains in the samples analyzed. 226Ra and 232Th showed a positively significant correlation with Mn, Ti, and S, while they showed a negative correlation with organic C at the significance level of r = −0.892 and r = −0.988, respectively. 40K exhibited a positive correlation with Si, Al, Na, P, and Mn (and, of course, with oxide K2O), suggesting that they have a common origin. Furthermore, a negative correlation was observed between the radionuclide 40K and Ca (r = −0.962). Since this element is highly abundant in seashells and eggshells, it confirms that materials containing it will have a low radioactivity concentration of 40K.
Concentrations of elements were also tested for any correlation with the physicochemical properties of the materials. Most elements were significantly correlated with each other. Iron was significantly correlated with Si and Al (r = 0.959 and r = 0.984, respectively). From the results, it can be concluded that Ca concentration has a strong negative correlation with Mg, Na, K, and P content. In the case of CS, it had a strong positive correlation with Mn (r = 0.927) and S (r = 0.945). The CS content also showed a strong correlation with 238U content.

4. Conclusions

The density and compressive strength of road-base binders decreased when different wastes were added in every proportion. Additions of 7.5% of both shells reduce the density to about 2.5% and the compressive strength to 20%, while 80% reduces the density to 20% and the compressive strength to 90%, while the addition of biomass fly ashes decreases the density and compressive strength in a higher proportion than shells. For all wastes, only a waste content of 7.5% satisfies the mechanical requirement for normal hardening road-base binders. Acid attack coefficients are increased when the three wastes are used, and this increase is greater when the waste dosage is increased (1500% more for biomass ash and 1000% higher for both shells)
With respect to leaching, scallop and eggshells can be considered inert wastes and can be used as a component of construction materials in accordance with Italian or Spanish regional limits. Fly ash from the combustion of olive pomace can be considered non-hazardous waste. It presents leaching values higher than Italian limits (Se, Pb, Ni, Mo, Cu, and As) and could not be used as a material in construction material according to all the different limits.
From a radiological perspective, all specimens showed activity concentrations for 226Ra and 232Th lower than the activity concentration for concrete. Only olive pomace ash showed higher values for 40K than the EU average, producing road-base binders with an activity concentration index higher than 1. Therefore, its use would not be recommended. No specimens show Raeq higher than the recommended value.

Author Contributions

Conceptualization, C.L. and S.H.-B.; methodology, J.L.M.; validation, B.P.; formal analysis, M.V.-A.; investigation, B.P.; resources, B.A.-F. and C.L.; data curation, S.H.-B.; writing—original draft preparation, J.L.M.; writing—review and editing, M.V.-A.; supervision, B.A.-F.; project administration, B.P.; funding acquisition, M.V.-A. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Regional Government of Coquimbo’s Innovation Funds for Competitiveness under grant number BIP 40014353-0 (Chile) and the Spanish National Plan 2017-2020 under grant number: PID2019-110928RB-C33 (Spain).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Iwański, M.; Buczyński, P.; Mazurek, G. Optimization of the road binder used in the base layer in the road construction. Constr. Build. Mater. 2016, 124, 1044–1054. [Google Scholar] [CrossRef] [Green Version]
  2. Cherian, C.; Siddique, S. Engineering and environmental evaluation for utilization of recycled pulp mill fly ash as binder in sustainable road construction. J. Clean. Prod. 2021, 298, 126758. [Google Scholar] [CrossRef]
  3. Vanhanen, H.; Dahl, O.; Joensuu, S. Utilization of wood ash as a road construction material-sustainable use of wood ashes. Sustain. Environ. Res. 2014, 24, 457–465. [Google Scholar]
  4. Zhao, Y.; Wu, P.; Qiu, J.; Guo, Z.; Tian, Y.; Sun, X.; Gu, X. Recycling hazardous steel slag after thermal treatment to produce a binder for cemented paste backfill. Powder Technol. 2022, 395, 652–662. [Google Scholar] [CrossRef]
  5. EN 13282-2:2016; Hydraulic Road Binders—Part 2: Normal Hardening Hydraulic Road Binders—Composition, Specifications, and Conformity Criteria. UNE: Madrid, Spain, 2016.
  6. Sharma, P.; Gaur, V.K.; Gupta, S.; Varjani, S.; Pandey, A.; Gnansounou, E.; Wong, J.W.C. Trends in mitigation of industrial waste: Global health hazards, environmental implications, and waste derived economy for environmental sustainability. Sci. Total Environ. 2022, 81, 152357. [Google Scholar] [CrossRef] [PubMed]
  7. Secher, A.Q.; Collin, C.; Linnet, A. Construction Product Declarations and Sustainable Development Goals for Small and Medium Construction Enterprises. Procedia CIRP 2018, 69, 54–58. [Google Scholar] [CrossRef]
  8. Mas, J.L.; Caro Ramírez, J.R.; Hurtado Bermúdez, S.; Leiva Fernández, C. Assessment of natural radioactivity levels and radiation exposure in new building materials in Spain. Radiat. Prot. Dosim. 2012, 194, 178–185. [Google Scholar] [CrossRef] [PubMed]
  9. Yan, N.; Chen, X. Sustainability: Don’t waste seafood waste. Nature 2015, 524, 155–157. [Google Scholar] [CrossRef] [Green Version]
  10. Martínez-García, C.; González-Fonteboa, B.; Martínez-Abella, F.; Carro-López, D. Performance of mussel shell as aggregate in plain concrete. Constr. Build. Mater 2017, 139, 570–583. [Google Scholar] [CrossRef]
  11. Peceño, B.; Alonso-Fariñas, B.; Vilches, L.F.; Leiva, C. Study of seashell waste recycling in fireproofing material: Technical, environmental, and economic assessment. Sci. Total Environ. 2012, 790, 148102. [Google Scholar] [CrossRef]
  12. Nguyen, T.A.H.; Ngo, H.H.; Guo, W.S.; Nguyen, T.T.; Vu, N.D.; Soda, S.; Nguyen, T.H.H.; Nguyen, M.K.; Tran, T.V.H.; Dang, T.T.; et al. White hard clam (Meretrix lyrata) shells as novel filter media to augment the phosphorus removal from wastewater. Sci. Total Environ. 2020, 741, 140483. [Google Scholar] [CrossRef]
  13. Ribeiro, J.C.A.; Vasques, I.C.F.; Teodoro, J.C.; Guerra, M.B.B.; Da Silva Carneiro, J.S.; Melo, L.C.A.; Guilherme, L.R.G. Fast and effective arsenic removal from aqueous solutions by a novel low-cost eggshell byproduct. Sci. Total Environ. 2021, 783, 147022. [Google Scholar] [CrossRef] [PubMed]
  14. Pérez-Villarejo, L.; Eliche-Quesada, D.; Carrasco-Hurtado, B.; Sánchez-Soto, P.J. Valorization of Olive Biomass Fly Ash for Production Eco Friendly Ceramic Bricks. In Encyclopedia of Renewable and Sustainable Materials; Elsevier: Amsterdam, The Netherlands, 2020; pp. 285–294. [Google Scholar] [CrossRef]
  15. Erses Yay, A.S.; Birinci, B.; Açıkalın, S.; Yay, K. Hydrothermal carbonization of olive pomace and determining the environmental impacts of post-process products. J. Clean. Prod. 2021, 315, 128087. [Google Scholar] [CrossRef]
  16. Tan, Y.Y.; Doh, S.I.; Chin, S.C. Eggshell as a partial cement replacement in concrete development. Mag. Concr. Res. 2018, 70, 662–670. [Google Scholar] [CrossRef]
  17. Sathiparan, N. Utilization prospects of eggshell powder in sustainable construction material—A review. Constr. Build. Mater. 2021, 293, 123465. [Google Scholar] [CrossRef]
  18. Her, S.; Park, T.; Zalnezhad, E.; Bae, S. Synthesis and characterization of cement clinker using recycled pulverized oyster and scallop shell as limestone substitutes. J. Clean. Prod. 2021, 278, 123987. [Google Scholar] [CrossRef]
  19. Her, S.; Park, J.; Li, P.; Bae, S. Feasibility study on the utilization of pulverized eggshell waste as an alternative to limestone in raw materials for Portland cement clinker production. Constr. Build. Mater. 2022, 324, 126589. [Google Scholar] [CrossRef]
  20. Peceño, B.; Arenas, C.; Alonso-Fariñas, B.; Leiva, C. Substitution of Coarse Aggregates with Mollusk-Shell Waste in Acoustic-Absorbing Concrete. J. Mater. Civ. Eng. 2019, 31, 0002719. [Google Scholar] [CrossRef]
  21. Peceño, B.; Leiva, C.; Alonso-Fariñas, B.; Gallego-Schmid, A. Is recycling always the best option? Environmental assessment of recycling of seashell as aggregates in noise barriers. Processes 2020, 8, 8070776. [Google Scholar] [CrossRef]
  22. Martínez-García, C.; González-Fonteboa, B.; Carro-López, D.; Pérez-Ordóñez, J.L. Assessment of mussel shells building solutions: A real-scale application. J. Build. Eng. 2021, 44, 102635. [Google Scholar] [CrossRef]
  23. Lila, K.; Belaadi, S.; Solimando, R.; Zirour, Z.R. Valorisation of organic waste: Use of olive kernels and pomace for cement manufacture. J. Clean. Prod. 2020, 277, 123703. [Google Scholar] [CrossRef]
  24. Fernández-Pereira, C.; De La Casa, J.A.; Gómez-Barea, A.; Arroyo, F.; Leiva, C.; Luna, Y. Application of biomass gasification fly ash for brick manufacturing. Fuel 2011, 90, 220–232. [Google Scholar] [CrossRef]
  25. Vilches, L.F.; Leiva, C.; Vale, J.; Olivares, J.; Fernández-Pereira, C. Fire resistance characteristics of plates containing a high biomass-ash proportion. Ind. Eng. Chem. Res. 2007, 46, 4824–4829. [Google Scholar] [CrossRef]
  26. Leiva, C.; Gómez-Barea, A.; Vilches, L.F.; Ollero, P.; Vale, J.; Fernández-Pereira, C. Use of biomass gasification fly ash in lightweight plasterboard. Energy Fuels 2007, 21, 361–367. [Google Scholar] [CrossRef]
  27. Cheboub, T.; Senhadji, Y.; Khelafi, H.; Escadeillas, G. Investigation of the engineering properties of environmentally friendly self-compacting lightweight mortar containing olive kernel shells as aggregate. J. Clean. Prod. 2020, 249, 119406. [Google Scholar] [CrossRef]
  28. Ashkoo, A.; Amininasab, S.M.; Zamani-Ahmadmahmoodi, R. Bioaccumulation of heavy metals in eggshell and egg content of seabirds: Lesser (Thalasseus bengalensis) and Greater Crested Tern (Thalasseus bergii). Mar. Pollut. Bull. 2020, 154, 111126. [Google Scholar] [CrossRef] [PubMed]
  29. Orłowski, G.; Kasprzykowski, Z.; Dobicki, W.; Pokorny, P.; Wuczyński, A.; Polechoński, R.; Mazgajski, T.D. Residues of chromium, nickel, cadmium, and lead in Rook Corvus frugilegus eggshells from urban and rural areas of Poland. Sci Total Environ 2014, 490, 1057–1064. [Google Scholar] [CrossRef] [PubMed]
  30. El-Sorogy, A.S.; Youssef, M. Assessment of heavy metal contamination in intertidal gastropod and bivalve shells from central Arabian Gulf coastline, Saudi Arabia. J. Afr. Earth Sci. 2015, 111, 41–53. [Google Scholar] [CrossRef]
  31. EN 197-1:2011; Cement Part 1: Composition, Specifications and Conformity Criteria for Common Cements. UNE: Madrid, Spain, 2011.
  32. ASTM D3682-21; Standard Test Method for Major and Minor Elements in Combustion Residues from Coal Utilization Processes. ASTM International: West Conshohocken, PA, USA, 2013.
  33. ASTM D854-14; Standard Test Methods for Specific Gravity of Soil Solids by Water Pycnometer. ASTM International: West Conshohocken, PA, USA, 2014.
  34. EN 1936:2006; Natural Stone Test Methods—Determination of Real Density and Apparent Density, and of Total and Open Porosity. UNE: Madrid, Spain, 2006.
  35. EN 196-1:2018; Methods of Testing Cement—Part 1: Determination of Strength. UNE: Madrid, Spain, 2018.
  36. Leiva, C.; Arenas, C.; Vilches, L.F.; Arroyo, F.; Luna-Galiano, Y. Assessing durability properties of noise barriers made of concrete incorporating bottom ash as aggregates. Eur. J. Environ. Civ. Eng. 2019, 23, 1485–1496. [Google Scholar] [CrossRef]
  37. EN 12457-4:2003; Characterisation of Waste—Leaching—Compliance Test for Leaching of Granular Waste Materials and Sludges—Part 4: One Stage Batch Test at a Liquid to Solid Ratio of 10 L/kg for Materials with Particle Size Below 10 mm (Without or with Size Reduction). UNE: Madrid, Spain, 2003.
  38. Council Directive 1999/31/EC of 26 April 1999 on the Landfill of Waste.European Commission. 1999. Available online: http://data.europa.eu/eli/dir/1999/31/oj (accessed on 8 March 2022).
  39. Waste Disposal at Landfills. Transposition to the Portuguese Law of Council; Directive 1999/31/CE, April 26, DL 183/2009; Portuguese Mint and Official Printing Office: Lisbon, Portugal, 2009.
  40. Ministero dell’Ambiente e della Tutela del Territorio. Decreto 5 Aprile 2006, n 186. Regolamento Recante Modifiche al Decreto Ministeriale 5 Febbraio 1998 “Individuazione dei Rifiuti non Pericolosi Sottoposti alle Procedure Semplificate di Recupero, ai Sensi degli Articoli 31 e 33 del Decreto Legislativo 5 febbraio 1997, n. 22”; GU Serie Generale n.115 del 19-05-2006; Gazzeta Ufficiale: Rome, Italy, 2006; Available online: https://www.gazzettaufficiale.it/eli/id/2006/05/19/006G0202/sg (accessed on 25 January 2023).
  41. Generalitat de Catalunya. DECRETO 32/2009, de 24 de Febrero, Sobre la Valorización de Escorias SiderúrgicasGeneralitat de Catalunya: Barcelona, Spain, 2003; Available online: https://vlex.es/vid/valorizacion-escorias-siderurgicas-81679082 (accessed on 25 January 2023).
  42. Decreto 34 Del País Vasco (2003), por el Que SE Regula la Valorización y Posterior Utilización de Escorias Procedentes de la Fabricación de Acero en Hornos de Arco Eléctrico, en El Ámbito de la Comunidad Autónoma Del País Vasco; Gobierno del Pais Vasco: Vitoria, Spain, 2003; (accessed on 25 January 2023).
  43. Kovler, K. Radiological constraints of using building materials and industrial by-products in construction. Constr. Build. Mater. 2009, 23, 246–253. [Google Scholar] [CrossRef]
  44. Nuccetelli, C.; Pontikes, Y.; Leonardi, F.; Trevisi, R. New perspectives and issues arising from the introduction of (NORM) residues in building materials: A critical assessment on the radiological behaviour. Constr. Build. Mater. 2015, 82, 323–331. [Google Scholar] [CrossRef]
  45. Council of the European Union. Council Directive 2013/59/Euratom of 5 December 2013 Laying Down Basic Safety Standards for Protection against the Dangers Arising from Exposure to Ionising Radiation. 2013. Available online: https://eur-lex.europa.eu/eli/dir/2013/59/oj (accessed on 7 February 2023).
  46. Lépy, M.C.; Altzitzoglou, T.; Anagnostakis, M.J.; Capogni, M.; Ceccatelli, A.; De Felice, P.; Yang, M.J. Intercomparison of methods for coincidence summing corrections in gamma-ray spectrometry—Part II (volume sources). Appl. Radiat. Isot. 2012, 70, 2112–2118. [Google Scholar] [CrossRef]
  47. ISO 11929-4:2022; Determination of the Characteristic Limits (Decision Threshold, Detection Limit and Limits of the Coverage Interval) for Measurements of Ionizing Radiation—Fundamentals and Application—Part 4: Guidelines to Applications. ISO: Geneva, Switzerland, 2022.
  48. Vidmar, T.; Aubineau-Laniece, I.; Anagnostakis, M.J.; Arnold, D.; Brettner-Messler, R.; Budjas, D.; Vidmar, G. An intercomparison of Monte Carlo codes used in gamma-ray spectrometry. Appl. Radiat. Isot. 2008, 66, 764–768. [Google Scholar] [CrossRef] [PubMed]
  49. United Nations Scientific Committee on the Effects of Atomic Radiation (UNSCEAR). Sources and Effects of Ionizing Radiation. Report to the General Assembly, with Scientific Annexes. Annex B. Exposures from Natural Radiation Sources. 2000. Available online: http://www.unscear.org/unscear/en/publications/2000_1.html (accessed on 25 January 2023).
  50. European Commission. Radiation Protection 112—Radiological Protection Principles Concerning the Natural Radioactivity of Building Materials, Directorate General Environment, Nuclear Safety and Civil Protection; European Commission: Brussels, Belgium, 1999. [Google Scholar]
  51. Organisation for Economic Co-Operation and Development (OECD); NEA Group of Experts. Exposure to Radiation from Natural Radioactivity in Building Materials; OECD Nuclear Energy Agency: Paris, France, 1979. [Google Scholar]
  52. Bonavetti, V.; Donza, H.; Menendez, G.; Cabrera, O.; Irassar, E.F. Limestone filler cement in low w/c concrete: A rational use of energy. Cem. Concr. Res. 2003, 33, 865–871. [Google Scholar] [CrossRef]
  53. Tayeh, B.A.; Hadzima-Nyarko, M.; Zeyad, A.Z.; Al-Harazin, S.Z. Properties and durability of concrete with olive waste ash as a partial cement replacement. Adv. Concr. Cons. 2021, 11, 59–71. [Google Scholar] [CrossRef]
  54. Baloochi, H.; Marilda Barra, D.A. Waste paper ash as a hydraulic road binder: Hydration, mechanical and leaching considerations. J. Environ. Manag. 2022, 314, 115042. [Google Scholar] [CrossRef]
  55. Deqiang, Z.; Bingliu, Z.; Weiguo, S.; Miaomiao, W.; Yecheng, G.; Jiale, W.; Zheng, Z.; Jiaoqun, Z. High industrial solid waste road base course binder: Performance regulation, hydration characteristics and practical application. J. Clean. Prod. 2021, 313, 127879. [Google Scholar] [CrossRef]
  56. Leiva, C.; García Arenas, C.; Vilches, L.F.; Vale, J.; Gimenez, A.; Ballesteros, J.C.; Fernández-Pereira, C. Use of FGD gypsum in fire resistant panels. Waste Manag. 2010, 30, 1123–1129. [Google Scholar] [CrossRef] [PubMed]
  57. Vafaei, M.; Allahverdi, A.; Dong, P.; Bassim, N. Acid attack on geopolymer cement mortar based on waste-glass powder and calcium aluminate cement at mild concentration. Constr. Build. Mater. 2018, 193, 363–372. [Google Scholar] [CrossRef]
  58. Ríos, J.D.; Arenas, C.; Cifuentes, H.; Vilches, L.F.; Leiva, C. Development of a paste for passive fire protection mainly composed of granulated blast furnace slag. Environ. Prog. Sustain. Energy 2020, 39, e13382. [Google Scholar] [CrossRef]
  59. Trevisi, R.; Risica, S.; D’Alessandro, M.; Paradiso, D.; Nuccetelli, C. Natural radioactivity in building materials in the European Union: A database and an estimate of radiological significance. J. Environ. Radioact. 2012, 105, 11–20. [Google Scholar] [CrossRef] [PubMed]
  60. Salazar, P.A.; Leiva, C.; Luna-Galiano, Y.; Villegas, R.; Fernández-Pereira, C. Physical, Mechanical and Radiological Characteristics of a Fly Ash Geopolymer Incorporating Titanium Dioxide Waste as Passive Fire Insulating Material in Steel Structures. Materials 2022, 15, 8493. [Google Scholar] [CrossRef] [PubMed]
  61. Leiva, C.; Arroyo-Torralvo, F.; Luna-Galiano, Y.; Villegas, R.; Vilches, L.F.; Fernández Pereira, C. Valorization of Bayer Red Mud in a Circular Economy Process: Valuable Metals Recovery and Further Brick Manufacture. Processes 2022, 10, 2367. [Google Scholar] [CrossRef]
  62. Leiva, C.; Arenas, C.; Cifuentes, H.; Vilches, L.F.; Rios, J.D. Radiological, leaching, and mechanical properties of co-combustion fly ash in cements. J. Hazard. Toxic Radioact. Waste 2017, 21, 04017011. [Google Scholar] [CrossRef]
Applsci 13 01644 g001 550
Figure 1. Particle size distribution of scallop shells, eggshells, and fly ash from olive pomace combustion.
Figure 1. Particle size distribution of scallop shells, eggshells, and fly ash from olive pomace combustion.
Applsci 13 01644 g001
Applsci 13 01644 g002 550
Figure 2. Gamma-ray spectrometry setup showing the measuring geometries with a cylinder specimen viewed from the top (left), and a cylinder specimen viewed from the side (right).
Figure 2. Gamma-ray spectrometry setup showing the measuring geometries with a cylinder specimen viewed from the top (left), and a cylinder specimen viewed from the side (right).
Applsci 13 01644 g002
Applsci 13 01644 g003 550
Figure 3. Resistance to the acid attack of hydraulic road binders. Note: CP: Portland cement; SC: scallop shells; E: eggshell; OR: biomass fly ash.
Figure 3. Resistance to the acid attack of hydraulic road binders. Note: CP: Portland cement; SC: scallop shells; E: eggshell; OR: biomass fly ash.
Applsci 13 01644 g003
Applsci 13 01644 g004 550
Figure 4. Specimens (a) before, (b) after acid attack, and (c) CP-20-OR-80 after acid attack and compressive strength testing.
Figure 4. Specimens (a) before, (b) after acid attack, and (c) CP-20-OR-80 after acid attack and compressive strength testing.
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Applsci 13 01644 g005 550
Figure 5. Heat map of Pearson’s r correlation values of activity concentration and physicochemical com-position of building samples with significance level expressed by asterisks (*** p-value ≤ 0.001, ** p-value ≤ 0.05, * p-value ≤ 0.1).
Figure 5. Heat map of Pearson’s r correlation values of activity concentration and physicochemical com-position of building samples with significance level expressed by asterisks (*** p-value ≤ 0.001, ** p-value ≤ 0.05, * p-value ≤ 0.1).
Applsci 13 01644 g005
Table
Table 1. Main chemical components (% weight) of Portland cement, scallop shells, eggshells, and olive oil pomace ash. Note: CP: Portland cement; SC: scallop shells; E: eggshell; OR: fly ashes; LOI: loss on ignition.
Table 1. Main chemical components (% weight) of Portland cement, scallop shells, eggshells, and olive oil pomace ash. Note: CP: Portland cement; SC: scallop shells; E: eggshell; OR: fly ashes; LOI: loss on ignition.
CPSCEOR
SiO2 (%)13.80.010.626.8
Al2O3 (%)3.50.040.076.8
Fe2O3(%)2.3-0.65.2
MnO (%)0.10.04-5.6
MgO (%)0.7-0.45.1
CaO (%)59.354.062.416.4
Na2O (%)0.10.5-1.5
K2O (%)0.5-0.222.5
TiO2 (%)0.2---
P2O5 (%)0.10.1--
SO3 (%)1.70.31.3-
LOI (%)15.543.234.49.4
Specific Density (g/cm3)3.192.632.642.73
Table
Table 2. Tested compositions. Note CP: Portland cement; SC: scallop shells; E: eggshell; OR: biomass fly ash.
Table 2. Tested compositions. Note CP: Portland cement; SC: scallop shells; E: eggshell; OR: biomass fly ash.
CompositionCement (%)Waste
(%)		Water/Solid Ratio
CP-100100-0.35
CP-92.5-SC-7.592.57.5
CP-20-SC-802080
CP-92.5-E-7.592.57.5
CP-20-E-802080
CP-92.5-OR-7.592.57.5
CP-20-OR-802080
Table
Table 3. Physical and mechanical properties Note: CP: Portland cement; SC: scallop shells; E: eggshell; OR: biomass fly ash.
Table 3. Physical and mechanical properties Note: CP: Portland cement; SC: scallop shells; E: eggshell; OR: biomass fly ash.
CompositionDensity (kg/m3)CS (MPa)
CP-1001857 ± 2242.6 ± 1.2
CP-92.5-SC-7.51813 ± 2137.8 ± 1.3
CP-20-SC-801449 ± 172.5 ± 0.3
CP-92.5-E-7.51800 ± 2533.2 ± 0.9
CP-20-E-801507 ± 182.6 ± 0.3
CP-92.5-OR-7.51846 ± 1923.3 ± 0.8
CP-20-OR-801651 ± 111.4 ± 0.2
Table
Table 4. Results of EN 12457-4 leachability test and limits stated in the European landfill directive and Italian regulations.
Table 4. Results of EN 12457-4 leachability test and limits stated in the European landfill directive and Italian regulations.
Leaching Limit (mg/kg, Dry Base)Leaching Results (mg/k, Dry Base)
1999/31/Ec [41]Italian limits [43]
ElementHazardNon-hazardousInert and Portuguese limit [42]CementScallop shellEggshellBiomass
fly ash
Zn2005040.031.1≤0.03≤0.030.02
Se70.50.10.1≤0.1≤0.1≤0.10.4
Sb50.70.06-≤0.1≤0.1≤0.10.2
Pb50100.50.5≤0.1≤0.1≤0.19.2
Ni40100.40.1≤0.1≤0.1≤0.11.2
Mo30100.5-≤0.10.20.71.7
Hg20.20.010.01≤0.1<0.1<0.1<0.1
Cu1005020.50.50.10.86.5
Cr (total)70100.50.50.6<0.2<0.2<0.2
Cd510.040.05<0.03<0.03<0.03<0.03
Ba30010020100.40.91.20.3
As2520.50.5≤0.3≤0.3≤0.31.7
Table
Table 5. Activity concentrations (Bq/kg) of 40K, 226Ra, and 232Th. Note: CP: Portland cement; SC: scallop shells; E: eggshell; OR: biomass fly ash.
Table 5. Activity concentrations (Bq/kg) of 40K, 226Ra, and 232Th. Note: CP: Portland cement; SC: scallop shells; E: eggshell; OR: biomass fly ash.
Specimens40K 226Ra 232Th
CP-100192 ± 930.5 ± 1.323.9 ± 3.2
CP-20-E-8046.4 ± 38.2 ± 0.55.3 ± 0.4
CP-20-SC-8053.3 ± 5.67.5 ± 0.45.1 ± 0.5
CP-20-OR-803683 ± 15418.8 ± 1.820.6 ± 1.5
CP-92.5-E-7.5179 ± 927.6 ± 1.219.2 ± 1.2
CP-92.5-SC-7.5176 ± 929.8 ± 1.220.4 ± 1.2
CP-92.5-OR-7.5449 ± 1927.6 ± 1.720.6 ± 1.7
Table
Table 6. Activity concentration index (I), radium equivalent activity (Raeq), absorbed (D), and effective dose rate (E). Note: CP: Portland cement; M: scallop shells; E: eggshell; OR: biomass fly ash.
Table 6. Activity concentration index (I), radium equivalent activity (Raeq), absorbed (D), and effective dose rate (E). Note: CP: Portland cement; M: scallop shells; E: eggshell; OR: biomass fly ash.
SpecimensIRaeq (Bq/kg)D
(nGy/h by Bq/kg)		E
(mSv/y)
CP-1000.29 ± 0.02 79.536.50.179
CP-20-E-800.07 ± 0.0119.48.90.044
CP-20-SC-800.07 ± 0.0118.98.80.043
CP-20-OR-801.39 ± 0.06331.8174.70.857
CP-92.5-E-7.50.25 ± 0.0368.831.80.156
CP-92.5-SC-7.50.26 ± 0.0372.533.40.164
CP-92.5-OR-7.50.34 ± 0.0491.643.90.215
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Peceño, B.; Hurtado-Bermudez, S.; Alonso-Fariñas, B.; Villa-Alfageme, M.; Más, J.L.; Leiva, C. Recycling Bio-Based Wastes into Road-Base Binder: Mechanical, Leaching, and Radiological Implications. Appl. Sci. 2023, 13, 1644. https://doi.org/10.3390/app13031644

AMA Style

Peceño B, Hurtado-Bermudez S, Alonso-Fariñas B, Villa-Alfageme M, Más JL, Leiva C. Recycling Bio-Based Wastes into Road-Base Binder: Mechanical, Leaching, and Radiological Implications. Applied Sciences. 2023; 13(3):1644. https://doi.org/10.3390/app13031644

Chicago/Turabian Style

Peceño, B., S. Hurtado-Bermudez, B. Alonso-Fariñas, M. Villa-Alfageme, J. L. Más, and C. Leiva. 2023. "Recycling Bio-Based Wastes into Road-Base Binder: Mechanical, Leaching, and Radiological Implications" Applied Sciences 13, no. 3: 1644. https://doi.org/10.3390/app13031644

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