3.1. Macroalgal Biomass Sampling Survey
According to previous studies [
8,
25,
26], few marine biomass sampling surveys have been conducted. The macroalgae deposition area results (
Figure 3) were demarcated in vertical-band transects that were observed between 1 and 21 m along the shoreline.
The average was at 9 m, defining a demarcation area of 135,000 m
2. Regarding the seasonality of collections in the present study (
Table 2), there was greater macroalgae deposition in the months of March and April (dry season), in both of the years surveyed (2015 and 2016), and lower deposition in September and October. These latter months form a regional transition period between the rainy winter and dry summer. The survey results showed that the average daily deposition was 5.03 t/ha (
Figure 4). The potentially productive area of 135,000 m
2 (13.5 ha) therefore yielded an estimated an average daily deposition of 67.90 t/ha, which gives an annual projection of 24,785 t/ha of dry weight. Previously, significant results were found in the state of Bahia, with beach-cast seaweed deposition (dry weight) of 5765 g/m
2 in 2007 for Itapuã beach and 2269.7 g/m
2 for Pituba beach in 2010 [
10]. Another study [
27] conducted on four potential beaches in northeastern and southeastern Brazil, in the states of Ceará, Pernambuco and Espírito Santo, found that the average biomass deposition ranged from 732.0 to 1041.2 g/m
2, from four collections conducted in the months of February, March, May and June, in which taxonomic classification was also used with twelve species analyzed. In Brazil, “bloom” occurrence in three phyla comprising chlorophytes, rhodophytes and ochrophytes [
10,
28,
29] has been found to increase deposition in coastal areas. The evaluation of macroalgal deposition areas at high and low tide, taking the phases of the moon to be a strong deposition agent, has shown that major deposition occurs at the full and new moons. This productivity factor of macroalgal biomass can become greater at the daily periods of greatest deposition at low tide with collection twice a day according to the tide table. In this, collection can reach amounts of approximately 10.06 t/ha daily, i.e., a projection of 49,570 t/ha/year in the respective area. This enormous production comes with the invariable condition that marine macroalgal biomass is the only form of biomass worldwide from which two collections per day can be performed. This is an exponential advantage in comparison with terrestrial biomass.
On the other hand, macroalgal productivity in the coastal environment does not present deposition in continuous biomass bands. Empty sand intervals can be observed between transects, and this factor can therefore be considered to constitute a diminution of productivity.
In
Table 2, it can be seen that there was no biomass deposition at some collection points in September and October. This result confirms that in the rainy season, beaches without a geological fringe coral reefs presented less biomass deposition than beaches with great coral formation near the coast. These are characteristics of benthic macroalgae that reproduce more intensively through improved photosynthesis in summer while located on coral fringe rock barrier substrates, which then may become dislodged through the force of the tides [
30,
31,
32].
The most important biomass for food supply and biofuel in Brazil is sugarcane. Its annual productivity is 76.9 t/ha [
33], considering crop production per 18 months. However, the estimated macroalgal biomass deposition over the same period that could be obtained through just one daily collection would be 35 times greater than the amount of biomass from sugarcane production. Based on productivity of 5.03 t/day × 547.5 days (18 months), the amount of macroalgal biomass would be 2691.50 t/ha/year (
Figure 4). The main factor that differentiates the productivity of the respective biomasses is that sugarcane is harvested after eighteen months, while macroalgae can be collected daily [
34]. Other advantages of macroalgae as a raw material collected in coastal regions include the facts that it is obtained through a free process, i.e., without agricultural costs due to inputs or irrigation. On the other hand, there are costs relating to washing processes, sea sand decantation, the separation of rubbish residues, drying machines and teams of workers needed for gathering the material every day [
4,
25].
According to one-way ANOVA statistical analysis [
35,
36], significant differences occurred, which were mainly through the absence of biomass observed on the beaches of Guaxuma, Garça Torta and Sereia (
Table 2). The Newman–Kuels test [
37] indicated that there were differences in the amount of biomass among the four collections performed with the highest amount of biomass (1.948 kg/m
2) at Jatiúca beach (F = 5.774,
p < 0.05). Tukey’s test [
38] showed that there were significant differences in the amount of biomass in samples 1 and 2 compared with samples 3 and 4 (periods without macroalgal biomass deposition) (
Table 2).
3.3. Factors Involved in Macroalgal Deposition
Some depositional factors, such as photosynthesis, sea water tidal strength, ocean water temperature, surface aquatic nutrients, climatic variations and the extent of coral reefs, can change the biomass volume and deposition area [
39]. Photosynthesis is an element of sustainability for macroalgae growth and deposition along the coastline. The photosynthetic efficiency of marine macroalgae (6–8%) is superior to that of terrestrial biomass (1.8–2.2%) [
2,
40,
41]. This feature means that macroalgal biomass requires less energy to develop than terrestrial plants, which promotes the advantage of growing faster than any terrestrial plant species [
42,
43,
44].
Seasonal macroalgae collections in the summer can yield better results with high biomass deposition [
39,
45,
46,
47]. The macroalgae collected on beaches such as Ponta Verde reached productivity levels of 20.3 t/ha in summer (
Figure 6), with a discontinuous transect deposition area of 1.85 ha (
Figure 7). The average deposition (9.1 t/ha) (
Figure 6) shows that summer production is more pronounced. This can be attributed in part to the greater proximity of the sun to our planet in January (in the southern hemisphere), which is a period characterized as the “perihelion”. Better photosynthesis is favored through greater solar radiation and increased water temperature, creating better conditions for biomass reproduction [
37,
40,
48]. There is a 3.3% difference in the Earth–sun distance between the aphelion and perihelion [
49], which means that the top of the atmosphere intercepts about 6.7% more solar radiation at the perihelion than at the aphelion 50,51]. This factor increases the incident global solar radiation to an insolation rate of 6% in relation to the aphelion period in June. The Earth’s position at the summer solstice extends the length day in Maceió to 14 h 10 min, while at the winter solstice, it is 10 h 10 min. The perihelion factor may contribute to increasing the ocean water temperature [
50] and enabling a greater input of energy to macroalgae in their natural environment. This favors improvement of the conditions for better photosynthesis and facilitates the absorption of organic nutrients for macroalgae reproduction, which gives rise to their best development during this period.
Macroalgal species in tropical climates have a greater euphotic margin in the oceans. This combines favorably with the greater proximity to equatorial zone, such that the insolation rates in the northeastern region of Brazil yield 8 h in summer and 6 h in winter [
51]. This has consequences regarding photosynthesis variations, pigmentation, and nutrients associated with water temperature and morphological structure, leading to significant growth [
48,
52]. Because of the city of Maceió’s position in the tropical zone, it has intense solar radiation that enables the incidence of a large euphotic zone with low turbidity in coastal marine waters, which favors the appearance of algal species in the phylum Chlorophyta.
The sustainability of benthic species is conditioned by coral reef ecosystems (
Figure 8). In these, macroalgae are attached to rocks in accordance with their genetics and natural habitat. They are influenced by cyclical seasonality, such that they may have greater or lower exposure to solar radiation at different water temperatures [
19,
29,
52].
For Ponta Verde beach, with macroalgae deposition of 37.63 t/day and 13,737 t/year, even if an estimate of 50% average loss due to discontinuous areas is projected, the annual deposition may reach 6868 t/year. This percentage difference between continuous and discontinuous areas was assessed previously [
53], in a study conducted in Odawa Bay, Japan, on the macroalgal seagrass carpet species
Zostera marina Linnaeus,
Zostera japonica Ascherson & Graebner and
Halophila ovalis (R.Br.) Hook. Deposition varied by more than 100% across the research area. In an actual study, three random collections were carried out on Cruz das Almas and Jacarecica beaches, which do not have barrier reefs along their shorelines. A total absence of biomass deposition was observed on these beaches. This marginal coastal strip on the urban perimeter was displayed through different transects of biomass deposition. It represents relief transformations in the continental shelf region, in which marine macroalgae are found in different topographic formations. These irregular biomass accumulations interspersed along the coastal strip with sand may be associated with morphological accommodations of terrain and unequal arrangements of rocky beds in the barrier reef on these beaches. Prolonged coral formation favors benthic macroalgal development aggregated to the rocky substratum and provides ideal habitats for macroalgal growth (
Figure 8).
Another factor that may have an impact on the reproduction of marine macroalgae is dynamic ocean surface air masses, which may form different streams over water and provoke erosional forces on reefs that are the natural habitat of marine macroalgae. This continuous cyclical movement may accelerate the process of transporting marine benthic macroalgal biomass from the ocean surface to the shoreline. The influences of air masses and their climatic characteristics are defined as a “tropical coastal climate” in the northeastern region of Brazil. Climatic studies [
54] have characterized the wind regime in this region as one of trade winds that reach this area and blow toward the equator, deviating to the left due to Coriolis force and giving rise to southeasterly winds. In the area of the present study, winds blow predominantly from the east between September and April and from the southeast between May and August. In the summer season (from October to March), the wind speed can produce dynamic forces and displace floating marine biomass with greater intensity. In a previous study [
31], values between 6.94 and 10.19 m/s for northeasterly winds were obtained; in contrast, weaker southeasterly winds from 4.22 to 6.07 m/s were recorded, following the influence of the South Atlantic anticyclone region, from the late autumn, which marks the ending of the rainy season.
The influence of marine streams on macroalgal biomass deposition remains an abiotic system. Three marine streams have been investigated at the regional scale [
54]: the northern current of Brazil, coastal drift currents and tidal currents. These marine currents can move benthic macroalgae and disperse beach-cast seaweed along coastal beaches, causing greater biomass deposition. The relative dominance of each of these current systems at any given point will be determined mainly as a function of the distance from the coast and some aspects of coastal geometry. This means that further away from the shoreline, the influence of the northern current of Brazil will be increases. This current flows northwestwards, being driven by the prevailing trade winds from the southeast. Closer to the continental shelf, the influence of coastal drift and tidal currents becomes greater. The coastal drift has a preferential east-to-west direction, mainly motivated by coastline orientation, which along this stretch of the coast is east–west, such that waves that reach the coastline preferentially come from the northeast and east. Tidal currents are perpendicular to the shoreline and have an influence approximately as far as the 10 m isobath. The longshore drift is significant, with its main currents flowing west–northwest, induced by dominant forces with regular waves providing sediment transportation, comprising of the order of 100 m
3/day of marine biomass deposition to the west [
31,
32].
Macroalgal rafts with floating navigation characteristics are extensive on the surface of the Pacific Ocean and the eastern China Sea [
47,
52,
55]. In India, these species of “drifting seaweed” have been found to give rise to a deposition of 126.81 kg/km
2 (wet weight) over an area of 6.14 km
2. These have been classified as species of
Sargassum C. Agardh, and their characteristics of floating of the sea surface are due to gas storage vesicles in their membrane that enable them to remain on the surface [
19,
22].
Sargassum species with the same gas storage vesicles were found in the present study, in which 26 taxonomic macroalgal species were classified (
Table 3).
3.4. Macroalgal Thermal Capacity: HCV and LCV
Previous studies [
40] on macroalgae found that they presented HCV values of 17.6 MJ/kg and 21.7 MJ/kg, respectively. These results are superior to the HCV of many terrestrial biomasses. Pyrolysis on the macroalgal species
Laminaria japonica Areschoug,
Fucus serratus L. and
Porphyra tenera Kjellman, i.e., heating the macroalgal biomass to 500° C, showed HCV results of 33.57 MJ/kg, 32.46 MJ/kg and 29.74 MJ/kg, respectively [
56]. Thus, macroalgae show biodiversity in terms of diverse chemical compositions, treatment methodologies, seasonality, natural environment, endemic species and different genetic evolution. Hence, the energy potential will vary depending on the species evaluated [
4,
57]. The respective upper and lower calorific power of macroalgae were in the ranges 6.3–12 MJ/kg and 5.9–10.8 MJ/kg, i.e., below those of most terrestrial biomasses, which present HCV values of 17–18 MJ/kg [
2,
8]. However, in the present study, macroalgal biomass compounds with an average LCV of 8.82 MJ/kg were identified (
Table 4). This was similar to that of the main biomass in Brazil, sugarcane bagasse, which has a value of 8.91 MJ/kg [
46,
57]. Among the characteristics that have been compared between macroalgae and terrestrial biomass, the absence of lignin in the composition of macroalgae [
56,
58] increases its degradation and facilitates its combustion. However, the levels of carbon contrast and hydrogen molecules in terrestrial biomass are higher than those in macroalgal biomass [
52,
59], and these factors provide higher calorific power. On the other hand, a selected combination of species consisting of 25%
Sargassum sp., 35%
Cryptonemia crenulata, 10%
Gracilaria sp. and 30%
Sargassum vulgare may have an estimated HCV of 11.29 MJ/kg, i.e., about 11.2% higher than an aggregated compound of macroalgal biomass (10.03 MJ/kg). Thus, there is a possibility that the selective collections of species, or combinations of different biomasses of macroalgae, may give rise to better yields and greater energy potential [
60,
61,
62]. In another study [
63], the phyla Chlorophyta and Ochrophyta were found to have high calorific values of 8–13 MJ/kg and 9–11 MJ/kg respectively. Those results were equivalent to those of the present survey for species in the phyla
Chlorophyta and
Ochrophyta (
Table 4). The species of the phylum
Rhodophyta reached the highest calorific values of 11.4–12.0 MJ/kg.
3.4.1. Evaluation of Heat Capacity Produced by Pellets
Cylindrical pellets of diameter 3–5 mm and length 8–23 mm were produced with specific mass of 680 kg/m
3. Corn oil was input as a binder, of volume 50 mL, equivalent to 1.88 MJ/kg, with performance of 6 kg of dry biomass, thus resulting in 1.28 kg of pellets. The high calorific value (HCV) obtained was 20.19 MJ/kg (
Figure 9). The ligand participated in the PCS, representing 9.35%, plus the average biomass moisture (17.61%). The total calorific value of 26.96% was attributed to the binder and moisture. Corn oil was chosen because of the sustainability of this agricultural product, given that Brazil is the world’s third largest producer of corn, thus enabling a greater availability of raw material with low production costs. Corn oil can add nutritional value to the pellets produced without negative environmental impacts that could interfere with the production process. Studies [
3,
64,
65] have shown that increased abrasion resistance to reduce wear on equipment for producing biofuel pellets can be achieved through the addition of natural binders such as corn, potato starch, cane molasses, vegetable oil and sulfonated lignin (waste from the pulp and paper industry). It has been reported [
64,
65] that additive use should be analyzed cautiously because sulfonated lignin, for example, increases the sulfur content, which causes undesirable gas emissions when pellets are burned with environmental implications. There is no consensus about these binders. These additives are not used in the United States and Italy for high-quality pellets. In Sweden, the use of these binders must be informed on product packaging. Research carried out in Sweden [
64,
65] showed that producers used 0.5–2.0% potato starch in wood pellets. The ash content found in pellets is similar to that found in relation to macroalgal species. because it is the same raw material aggregated in a compound.
A comparison with the higher calorific value of terrestrial biomass [
60,
66] condensed into energetic composites such as in briquette form (
Figure 10) showed that it ranged from 9.83 to 20.51 MJ/kg with an average of around 17.61 MJ/kg. This was 11.46% lower than the higher calorific value of macroalgae aggregated into condensed pellets, as determined from five samples evaluated in the present study, which was 20.19 MJ/kg (
Figure 10). The lower calorific values of the pellets and briquettes were equivalent, without significant difference when analyzed for the same biomasses, given that the compression and moisture suppression processes for these two cylindrical formats are similar. The average HCV for terrestrial pellets (19.96 MJ/kg), as evaluated in two previous studies [
63,
67], was 1.15% lower than that of macroalgae pellets (20.19 MJ/kg) (
Table 5).
The average LCV of pellets from 17 terrestrial species was found to be 16.10 MJ/kg [
68], which was 11.6% lower than the average for macroalgae pellets (18.76 MJ/kg). Both indicators (HCV and LCV) showed that it was more efficient to generate energy using macroalgal biomass than using the majority of terrestrial pellets [
69]. The chemical structure and composition of the biomass underwent changes through pelletization. Likewise, the physical structure, such as the porosity and surface morphology of the biomass, are compacted in cylindrical concentrated compounds. Consequently, the thermal characteristics of biomass pellets differ from those of the feedstock that is received [
62].
3.4.2. Heat Capacity of Seaweed from Nutrient/Fiber Analysis
Materials with high carbon and hydrogen content keep high calorific value, while the presence of oxygen has the opposite effect [
70,
71]. The results from the present study confirm this theory. The macroalgal species
Ulva lactuca and
Hypnea pseudomusciformis have carbon concentrations of, respectively, 50.08% and 61.87%, which are the highest percentages of all types of macroalgal biomass. The HCV of
Ulva lactuca is 1.43 MJ/kg, which thus has potential for the energy industry (
Table 6). The high carbon content of some macroalgal species may be due to the presence of several sulfated polysaccharides (PSs) in their composition [
68]. Thus, the species
H. pseudomusciformis is characterized as a carrageenan. This family of PSs undergoes several variations originating from free hydroxyl substitutions. Repetitive disaccharide units form these polymers.
Macroalgae with low lignin content have reduced calorific values in relation to terrestrial biomasses and generally lower calorific values than those of biomasses with higher lignin content and high cellulose content [
72]. Lignin should be considered as having an average HCV (0.025 MJ/kg) compared with 0.015 MJ/kg for celluloses. It is known that a lignin polymer contains less oxygen than the polysaccharides present in cellulose [
59], which is a factor that influences the HCV. The species
Ulva lactuca has low lignin content (9.13%) (
Table 7) but was found to have the second largest HCV (11.43 MJ/kg). This was comparable with previous results from the same species, with HCV of 12.89 MJ/kg [
73], thus confirming the theory of low lignin x high calorific value.
The macroalgal ash content is higher than that of terrestrial biomass [
2,
40,
59]. In a previous study [
74], ash content ranging from 14 to 39.7% was found, among the 10 species that were analyzed, while a range from 3.3 to 46% was found among four species in another study [
75]. Those findings differed from the results from the present study in which the range was from 1.86 to 10.56% among 12 species that were analyzed (
Table 7). However, the species were not the same and may have physiologically distinct genetic development, which would influence their fiber concentrations. Variations in ash composition are influenced by seasonality [
40,
41], such that higher ash concentrations can be found at certain times of the year. The environmental impact of ash resulting from macroalgal combustion processes may vary depending on the specific characteristics of the ash and the context within which it is generated. The composition of macroalgal ash contains a variety of chemical elements, including oxides of silicon, aluminum, iron, calcium, potassium and magnesium [
76]. To mitigate environmental impacts, it is important to consider viable alternatives for reusing ash. Some studies have explored the possibility of using ash in other applications, such as construction materials or as soil-improver fertilizers [
77].
In summary, the environmental impact of macroalgal ash combustion depends on several factors, including the ash composition, treatment process and the way in which it is reused or discarded. It is important to consider strategies that minimize negative impacts and promote sustainability.
Reduced cellulose indices (11.28%) can facilitate combustion processes (
Table 7). According to previous studies [
72,
78], the cellulose glucose polymer is present in the macroalgae of the phyla Ochrophyta, Chlorophyta and Rhodophyta in amounts of less than 10%.