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Article

Evaluating the Liming Potential of Mytilus galloprovincialis Shell Waste on Acidic Soils

by
Alexios Lolas
1,2,*,
Katerina Molla
2,*,
Konstantinos Georgiou
1,
Chrysoula Apostologamvrou
1,
Alexandra Petrotou
1,
Konstantinos Skordas
1 and
Dimitris Vafidis
1
1
Laboratory of Marine Biology, Department of Ichthyology & Aquatic Environment, University of Thessaly, Fytokou Street, 38446 Volos, Greece
2
Hellenic Republic, Ministry of Rural Development and Food, Acharnon 2 Street, 10176 Athens, Greece
*
Authors to whom correspondence should be addressed.
Conservation 2024, 4(4), 778-791; https://doi.org/10.3390/conservation4040046
Submission received: 25 September 2024 / Revised: 19 November 2024 / Accepted: 21 November 2024 / Published: 2 December 2024
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Abstract

:
The sustainable management of aquaculture by-products is crucial for advancing circular economy practices. Mediterranean mussel shell waste, rich in calcium carbonate, presents a sustainable alternative to conventional liming materials, especially for mitigating soil acidification, a very important and common issue that limits crop productivity. This study evaluated the effectiveness of processed mussel shell waste in enhancing soil pH, organic matter, and nutrient availability. A 180-day pot experiment using highly acidic soil (pH < 4.5) collected from a local field was conducted in a Completely Randomized Design. Treatments involved two grain sizes of mussel shell powder (Fine: <1 mm; Coarse: 1–2 mm) at rates between 0.1 and 6%. Treated soil pH was measured monthly, whereas organic matter, available phosphorus (P), and exchangeable potassium (K) were measured at the beginning and the end of the experiment. The results revealed significant improvements in pH, organic matter, available phosphorus (P), and exchangeable potassium (K), particularly in the Fine Powder treatments. However, total nitrogen (N) remained unaffected. These findings highlight the potential of mussel shells as an eco-friendly and cost-effective amendment, advancing sustainable agriculture and waste recycling, thus contributing to broader conservation efforts by reducing the environmental footprint of aquaculture waste and supporting biodiversity and ecosystem resilience through sustainable resource management.

1. Introduction

Soil degradation is a multifaceted process that transitions a stable soil ecosystem to a more fragile and unstable state, often due to both unfavorable environmental conditions and extensive, improper human exploitation [1,2,3]. Typical forms of soil degradation include the loss of organic matter, deterioration of soil structure, decreased fertility, and acidification, all of which negatively affect crop production and pose broader environmental threats. Soil acidification, in particular, is becoming an emerging threat to the sustainability of global agricultural production. Several studies estimate that over 30% of the world’s ice-free land area consists of acidic soils (topsoil pH < 5.5) [4,5,6,7]. Although soil acidification can occur naturally due to prolonged rainfall and the leaching of basic cations (e.g., Ca2+ and Mg2+) from the topsoil, current rates of acidification have accelerated due to human activities, such as industrial emissions of sulfur and nitrogen oxides [8], as well as the extensive use of nitrogen-based fertilizers [5,6,7]. Beyond nutrient loss from decreased availability of basic cations [9], low pH conditions in the soil can facilitate the release of toxic elements like aluminum (Al) and manganese (Mn), which can damage plant roots, hinder growth, and reduce potential crop yields [10].
The most common practice for adjusting soil acidity is the use of materials containing calcium carbonate, such as marl, chalk, limestone, and hydrated lime (calcium and magnesium hydroxide). The most common practice for adjusting soil acidity is the use of materials containing calcium carbonate, such as marl, chalk, limestone, and hydrated lime (calcium and magnesium hydroxide [4,11,12]). For example, in South Africa, approximately 4.5 million metric tons of liming materials are used annually to amend soil acidity. Moreover, the extraction and processing of these calcification materials have significant environmental and economic impacts. Mining operations for limestone and chalk contribute to habitat destruction, loss of biodiversity, and increased carbon emissions, making this practice less sustainable. As a result, the use of such materials is not only inefficient but also economically unfeasible for resource-poor, small-scale farmers. These combined factors highlight the need for more sustainable and affordable alternatives to traditional liming methods [13,14].
In recent decades, significant research efforts have focused on finding alternative methods to improve acidic soils, particularly through the utilization of industrial waste products. This approach aligns closely with the principles of a circular economy, which emphasizes reducing waste, reusing resources, and recycling materials as a sustainable solution for managing resources more efficiently. One promising sector in this regard is aquaculture, especially mussel farming, which produces huge amounts of by-product waste in the form of discarded shells due to the need for further processing to extract the edible part for commercial packaging and human consumption [15,16,17]. Because mussel shells are primarily composed of calcium carbonate (CaCO3) along with smaller amounts of essential nutrients such as nitrogen (N), phosphorus (P), potassium (K), magnesium (Mg), and sodium (Na), they have been considered as a potential alternative source of CaCO3 in several sectors, such as construction as a substitute in cement and concrete production, cosmetics and pharmaceuticals, water treatment and, of course, agriculture [18,19,20,21,22,23,24,25,26]. Specifically, in the agriculture sector, instead of discarding materials like mussel shells into landfills, there is now a growing understanding of their potential as valuable resources for soil improvement. Utilizing these shells not only mitigates the environmental impact of aquaculture waste but also offers a cost-effective alternative to traditional lime materials, thus benefiting both agriculture and waste management sectors. This dual benefit supports sustainable agricultural practices by enhancing soil fertility while reducing the environmental footprint of aquaculture waste disposal [27].
Despite the potential of mussel shells as a liming material [17,25,28,29], there remains a lack of comprehensive research exploring their practical application in soil management, particularly in terms of optimizing the quantities and forms required to achieve soil pH adjustment and nutrient enhancement. This study aims to fill this gap by investigating the efficacy of Mediterranean mussel (Mytilus galloprovincialis) shells in amending acidic soils. Specifically, the research focuses on three primary objectives: (1) evaluating the potential of mussel shells as a sustainable alternative to conventional liming materials; (2) determining the optimal ratio of mussel shell application to rapidly increase soil pH to near-neutral levels; and (3) assessing the impact of different shell proportions on soil organic matter and the availability of key nutrients such as nitrogen (N), phosphorus (P), and potassium (K). By addressing these objectives, this study contributes to the broader understanding of how aquaculture by-products can be repurposed to support sustainable agriculture, thus aligning with circular economy principles and reducing reliance on non-renewable resources.

2. Materials and Methods

2.1. Sampling Process

Soil sampling was conducted in the rural area surrounding the city of Almyros (Thessaly, Greece) (Figure 1), which is known for its naturally acidic soils, as reported by local landowners and farmers. To determine the soil pH of a field, preliminary surveys were performed by taking measurements at three randomly selected spots within each field at a depth of 0–15 cm using a portable pH meter (C520 Multi-Parameter Analyzer, Consort). The average of these three measurements was used to represent the pH of each field. Approximately 30 fields with varying degrees of acidity were tested to identify the field with the lowest average pH. This field, having the most acidic conditions, was then selected for the experiment as it presented a more challenging scenario for evaluating the liming potential of mussel shells. Additional soil samples were subsequently collected from various locations across the selected field to ensure representative variability for the experiment.
Mediterranean mussel shells were sourced from a local seafood processing company. The mussels were pre-boiled, and their shells were removed during processing, as the edible portion was packed and frozen for consumer use. These shells, typically considered by-products, would normally be disposed of in a local landfill or incinerated. For this study, the collected mussel shells were rinsed with distilled water, placed on metallic plates, and exposed to airflow in an air dryer at 40 °C for 24 h. In rare cases where some moisture remained in the samples, we allowed the shells to dry for an additional 24 h to ensure complete moisture removal. After drying, the shells were ground using a mortar and pestle. The resulting shell powder was sieved through two stainless steel sieves with mesh sizes of 2 mm and 1 mm, resulting in two-grain textures: Fine Powder (FP, <1 mm) and Coarse Powder (CP, 1–2 mm).
Soil samples, after being air-dried at 70 °C, were sieved through a 2 mm sieve. The following physicochemical properties were measured at the beginning and at the end of the experiment, according to Rowell [30]. Soil pH was determined using a 1:2.5 soil–distilled water ratio (C520 Multi-Parameter Analyzer, Consort). The electrical conductivity value was measured using a 1:5 soil–distilled water ratio (SevenExcellence S470, Mettler Toledo). The percentages (%) of sand, clay, and slit were determined using the Bouyoukos method (Bouyoukos hydrometer). Organic matter was quantified using the Walkley–Black method (wet oxidation with 0.17 N K2Cr2O7, back-titrated with 0.5 M FeSO4). The total nitrogen (N) concentration in the extract was determined by the Kjeldahl method (Kjeldahl Pro-Nitro M, JP Selecta). Available soil phosphorus (P) was determined using the Olsen method by extraction with 0.5 M NaHCO3, and the measurement was conducted with a UV spectrophotometer at 882 nm (EMC-16PC-V model). Exchangeable potassium (K) was analyzed in a ratio of 1:10 by 1 M CH3COONH4 at pH 7.0, with measurements made using a flame photometer (Sherwood Model 410). Ground mussel shells from both grain sizes were similarly analyzed for pH, organic matter, total nitrogen, available phosphorus (P), and exchangeable potassium (K) using the same methods as those for the soil samples. Additionally, calcium carbonate (CaCO3) content in the mussel shells was analyzed using a Schreiber calcimeter (Calcis M, Lita Analytical).

2.2. Experimental Design and Analyses

The experiment was conducted on the campus of the Department of Ichthyology and Aquatic Environment (University of Thessaly, Greece), using square plastic pots (40 × 40 × 20 cm). For each grain size of ground mussel shells, CP and FP, six different application ratios were tested: 4, 12, 20, 40, 120, and 240 g of mussel shells per 4 kg of acidic soil, corresponding to 0.1%, 0.3%, 0.5%, 1%, 3%, and 6% ratios. An untreated pot with 4 kg of soil was used as the control. Each treatment was replicated in 10 pots, leading to a total of 130 pots. A Complete Randomized Design (CRD) was employed to allow for random assignment of treatments to eliminate bias and ensure the reliability of the results (Figure A1 in Appendix A).
The pots were placed in a storage room with an ambient temperature of 22–25 °C and watered every three days to maintain soil moisture at approximately 65%. Additionally, every two weeks, the soil was stirred using a small garden shovel to prevent the formation of lumps or crusts. Soil samples for pH measurements were collected from each pot at intervals of 30, 60, 90, 120, 150, and 180 days post-treatment.
In this study, Response Surface Methodology (RSM) was employed to predict maximum pH values based on varying mussel shell ratios and incubation days. The experimental design included Fine (<1 mm) and Coarse (1–2 mm) mussel shell powders and six different shell ratios (4, 12, 20, 40, 120, and 240 g per 4 kg of soil) as control variables, with maximum pH as the response variable. Response Surface Methodology (RSM) is a statistical and mathematical technique used to optimize and analyze complex processes [31,32]. It is particularly useful for understanding the interactions between multiple variables. Central Composite Design (CCD), a specific experimental design within RSM, integrates factorial points with additional axial and center points. This design enables quadratic model fitting and allows for the estimation of curvature in the response surface [33]. This approach was used to investigate how different mussel shell ratios and incubation days affect maximum pH values, with a second-order polynomial model fitted to the experimental data:
Y = β0 + β1X1 + β2X2 + β12X1X2 + β11X12 + β22X22
where:
  • β0, is constant;
  • β1, β2, β12, β11, β22, are regression coefficients,
  • X1, days of incubation and
  • X2, mussel shell ratios.
The experimental design for the RSM was structured using a CCD to effectively capture potential quadratic and interaction effects between factors and to allow for a comprehensive exploration of the response surfaces across the chosen factors. The analysis focused on two primary factors: Days of Incubation and Mussel Mass (g). Each factor was tested at multiple levels to capture a range of effects, with standard CCD setups typically including three levels (low, center, and high). This design choice enables the model to detect both linear and nonlinear relationships in the response variables (pH_Fine and pH_Coarse). The CCD structure in this experiment comprised 36 total experimental runs, which included replicates at the central points. These replicates improve the precision of the response model by allowing for the estimation of pure error. Replicates were also included at other points in the design to further enhance the reliability and accuracy of the model.
All statistical analyses were performed by the “STATGRAPHICS Centurion” software package (v.18.1.01, Statgraphics Technologies, Inc., The Plains, VA, USA), and values of p < 0.05 were considered significant.

3. Results

3.1. Physicochemical Properties of Soil and Mussel Shells

Among all sampled soils, the pH values ranged from a minimum of 4.26 to a maximum of 5.76. Apparently, the soil with the lowest pH value of 4.26 was selected for the experiments. The physicochemical properties of this soil are detailed in Table 1. The properties of the ground mussel shells, categorized by their different sizes, are presented in Table 2.

3.2. Effect on Soil pH

The application of various ground mussel shell ratios led to an overall increase in soil pH, as expected (Figure 2). However, the crucial factors were the rate of pH increase and the duration of the achieved pH values. Notably, the plots treated with 3% and 6% mussel shell mixtures exhibited the highest pH values among the treatments. Soil pH increased significantly and rapidly following the addition of 1% FP, 3% FP, and 6% FP, with increases of 1.47, 2.48, and 3.02 units compared to the control (pH 4.26), respectively (Figure 2A). After 180 days, the pH values for soil amended with FP were as follows: 7.23 (6% FP) > 7.19 (3% FP) > 6.97 (1% FP) > 6.64 (0.5% FP) > 6.09 (0.3% FP) > 5.74 (0.1% FP). Similarly, for CP, the pH values were: 7.44 (6% CP) > 7.10 (3% CP) > 6.32 (1% CP) > 5.81 (0.5% CP) > 5.61 (0.3% CP) > 5.46 (0.1% CP). Notably, the CP mussel shell led to a slower rate of pH increase compared to FP. At the end of the experiment (180 days), the 6% CP treatment resulted in a higher pH value (7.44) compared to the 6% FP treatment (7.23), as illustrated in Figure 2B. This indicates that while both powders were effective, FP achieved quicker pH adjustments.
Two models were developed using Response Surface Methodology (RSM) to optimize soil pH with FP and CP ground mussel shells, with the second-order polynomial model fitted to the experimental data represented by the following equations:
pH_Fine = 6.93375 + 0.03X1 + 1.05 X2 − 0.005 X1X2 + 0.0002 X12 + 0.08 X22
pH_Coarse = 5.445 + 1.0167 X1 + 0.7917 X2 − 0.805 X1X2 + 0.145 X12 −0.53 X22
where:
  • X1 represents Days of Incubation
  • X2 represents the Mussel Shell Ratio used
Both models demonstrated statistical significance with p-values less than 0.05 (Table 3), indicating that the models explain a significant portion of the variability in soil pH for both FP and CP. The results also confirm the strong predictive capability of the model, with only a small portion of the total variance attributed to the error term. The high F Ratio and very low p-value indicate that the model terms, including linear, interaction, and quadratic components, contribute significantly to explaining the observed pH response.
For the FP model, both linear and quadratic interactions of the independent variables significantly affected pH (p < 0.05). This model achieved an R2 value of 0.94 and a Root Mean Square Error (RMSE) of 0.29. In contrast, the CP model showed that the quadratic term for the days of incubation was not significant (p > 0.05), although all other interactions were highly significant (p < 0.05). This model had a higher R2 value of 0.96 and a lower RMSE of 0.22. The RSM results for pH are illustrated in Figure 3. For the model diagnostic plots, see Figure A2, Figure A3 and Figure A4 in Appendix A.

3.3. Effect on Soil Characteristics

Principal Component Analysis (PCA) was performed to assess correlations between soil properties across treatments (Figure 4). Factor loadings for each variable (organic matter, phosphorus, potassium, and nitrogen) indicated strong contributions from organic matter and phosphorus to the first principal component (PC1), explaining the 63.6% of the data variance, suggesting these two properties were most affected by mussel shell application. Exchangeable potassium and total nitrogen were more strongly associated with the second principal component (PC2), explaining 14.5% of the data variance. These PCA results imply that higher ratios of mussel shell contributed significantly to organic matter and phosphorus enhancements, while effects on potassium and nitrogen varied across treatments, pointing to possible nutrient-specific mechanisms influenced by shell composition.
More specifically, organic matter increased across all treatment doses following the application of the mussel shell. The highest values were observed in the 6% treatments, with 2.27% in Fine Powder pots and 2.09% in CP pots. Organic matter content was consistently higher in FP treatments than in CP, with the 6% FP treatment showing an 18% higher organic matter content than the 6% CP treatment. The concentration of available phosphorus (P) ranged from 23 mg kg−1 in the control pots to 46.2 mg kg−1 in the 6% FP pots. Statistically significant differences were observed between the treated and control pots (p < 0.05), except in the 0.1% CP treatment. The highest concentration of exchangeable potassium (K) was recorded in the 6% FP treatment (190.1 mg kg−1), while the lowest was in the 0.3% CP treatment (128.7 mg kg−1). Significant differences in exchangeable potassium were also found between the mussel shell treatments and the control (p < 0.05). Additionally, both available phosphorus and exchangeable potassium levels were slightly higher in the FP treatments compared to the CP treatments, with statistically significant differences noted.

4. Discussion

Soil acidity is a significant global agricultural challenge, affecting crop productivity, nutrient availability, and overall soil fertility [34]. Therefore, identifying alternative solutions to raise soil pH is of utmost importance. In this study, two different textures and six different ratios of ground mussel shells were applied to highly acidic soil, yielding promising results.
The decision to include both Fine Powder (FP) and Coarse Powder (CP) grain sizes in this study was based on a circular economy and sustainability approach. The finer texture of FP was expected to enhance soil pH more rapidly due to its increased surface area and faster dissolution rate. However, achieving this fine texture involves more intensive processing, which is resource- and energy-demanding. In contrast, CP requires significantly less processing, aligning better with sustainable practices by reducing energy consumption. By comparing the effectiveness of these two-grain sizes, we aimed to identify whether similar soil improvements could be obtained with a coarser, more resource-efficient product. Additionally, exploring the performance of different textures is crucial for the potential development of mussel shells as a key ingredient in specialized soil ameliorant products. Understanding how varying levels of shell processing influence soil properties can help optimize such products for agricultural use, providing tailored solutions for soil pH adjustment while minimizing production costs.
Given the alkaline nature of mussel shells, it was anticipated that their application to acidic soil would raise soil pH. This alkalinity is primarily due to the high calcium carbonate (CaCO3) content, a well-known agent for increasing pH [15]. In the current study, soil pH increased significantly, particularly at higher dosages (i.e., 1%, 3%, and 6% w/w). Eventually, by the end of the experiment, both Fine Powder (FP, <1 mm) and Coarse Powder (CP, 1–2 mm) achieved similar pH values at comparable dosages. However, FP raised pH more rapidly, nearing neutral (~7) within 30 days at higher dosages, whereas CP displayed a more gradual, linear increase, reaching pH 7 after around 150 days. The greater effectiveness of FP could be attributed to the finer texture of FP, which resulted in a greater surface area that likely enhanced the release of calcium carbonate (CaCO3) and other minerals upon contact with moisture, thus lowering the pH [35]. Furthermore, the mussel shells were not cleaned of their epibionts, which include a diverse array of organisms such as barnacles, polychaetes, coralline algae, and small bivalves [36]. The additional grinding of the FP fraction may have caused a more thorough breakdown of these CaCO3-rich epibiont structures, contributing to the observed higher initial CaCO3 content in FP compared to CP. As CaCO3 neutralizes hydrogen ions in acidic soils, it not only raises pH but also increases exchangeable calcium (Ca), improving nutrient availability, soil structure, and long-term fertility [37,38].
The differences in model performance, where the CP model demonstrated a higher R2 value and lower RMSE compared to the FP model, appear to support the approach of testing varying levels of processing. While FP resulted in quicker pH adjustments in absolute terms, CP provided more stable and consistent long-term performance. These differences may be due to several factors. One key factor could be the slower dissolution rate of CP. The coarser texture of CP leads to a more gradual release of calcium carbonate into the soil, resulting in a sustained and steady increase in soil pH over time. This gradual release may contribute to a more predictable and linear relationship between mussel shell concentration and pH changes, which aligns better with the assumptions of our model. Additionally, the coarser particles of CP might offer a better buffering effect in the soil matrix, minimizing pH fluctuations and leading to a more consistent response, thereby contributing to the higher R2 value observed. From a sustainability perspective, these findings are particularly meaningful. Although FP adjusts soil pH more rapidly, the additional processing required to achieve a finer grain size increases its energy consumption and environmental footprint. In contrast, it seems that CP can achieve comparable results with less processing, making it a more resource-efficient option. This aligns with the principles of the circular economy by promoting waste valorization and supporting sustainable agriculture through efficient resource reutilization.
In the context of Response Surface Methodology (RSM), the models developed for the FP and CP mussel shell treatments reveal important insights into how soil pH responds to incubation time and shell dosage. The constant term 5. represents the baseline pH when both incubation days and mussel shell weight are centered at their mean levels. The linear terms (i.e., aX1 and bX2) in the models indicate the direct, positive effects of both factors, meaning that increasing either incubation days or mussel shell ratios individually raises soil pH. The interaction terms (i.e., cX1X2) suggest that the combined influence of these two factors is more nuanced, potentially diminishing the rate of pH change when both variables are elevated simultaneously. Meanwhile, the quadratic terms (i.e., dX12 and eX22) highlight the nonlinear response, where pH increases tend to stabilize as the levels of incubation or shell ratio reach higher values, indicating diminishing returns beyond a certain point. These tailored equations are a useful tool by providing a predictive capability to anticipate pH changes under various combinations of shell ratio and incubation time. According to the RSM, by the end of the 180-day experiment, 64.6 g kg−1 of FP and 76.6 g kg−1 of CP M. galloprovincialis ground shells were sufficient to neutralize the highly acidic soil. In contrast, a similar study in Chile using Mytilus chilensis ground shells (grain size <1.7 mm) required 190 g kg−1 to achieve a pH close to 7.0 [39]. This represents a 68% higher requirement compared to the CP results and an even greater difference of 84% when compared to FP in this study. The greater efficiency observed here could be attributed to the finer particle size of FP, as well as differences in soil composition, initial pH levels, and possibly the contrasting climatic and environmental conditions between Chile and Greece. Several studies have highlighted the benefits of using CaCO3-rich shells (e.g., oysters, sea urchins, and mussels) in ratios ranging from 1 to 10% w/w, demonstrating their capacity to elevate soil pH across diverse environmental conditions [21,25,27,28,29,40,41]. While optimal shell quantities may vary locally, the broader implication is that the reutilization of mussel shells as a soil amendment is both effective and aligns with the goals of circular economy and agricultural sustainability.
Organic matter (OM) levels were positively influenced by the application of ground mussel shells, with higher dosages resulting in greater increases. FP performed better than CP, achieving a 47% increase in OM compared to the control at the 6% w/w ratio. The observed increase in OM may be partially attributed to the presence of epibionts, as mentioned previously, by contributing additional organic residues to the soil or as an indirect effect of the pH adjustment, especially given the known correlation between soil acidification and reduced organic matter decomposition, which inhibits soil microorganism activity [42]. Microbial biomass, a key component of soil organic matter, plays an essential role in the transformation and cycling of organic matter and nutrients. It serves as both a nutrient reservoir and an enzyme source, supporting plant growth [43]. The observed increase in OM also aligns with typical outcomes from liming treatments and can be attributed to several factors, such as enhanced OM solubility and increased microbial activity due to the reduction in biologically toxic aluminum (Al) levels [44,45].
This increase in OM was reflected in the PCA, where the first principal component (PC1), which explained 63.6% of the variance, showed strong positive factor loadings for organic matter (OM) and available phosphorus (P). These results suggest that OM and phosphorus were the most significantly impacted by mussel shell applications, highlighting their potential role in improving soil nutrient content. In contrast, the second principal component (PC2), which accounted for 14.5% of the variance, was more strongly associated with exchangeable potassium (K) and total nitrogen (N). This indicates that while OM and P were consistently enhanced, the effects on K and N were more variable across treatments, likely due to nutrient-specific dynamics and interactions with other soil properties.
Given that OM plays a crucial role in the terrestrial carbon and nitrogen cycles and significantly contributes to the availability of nutrients like N, P, and K, its increase can positively impact plant nutrient uptake. In this study, ground M. galloprovincialis shell application led to a marked increase in P and K levels, with FP performing better than CP. These findings are consistent with established research indicating that acidic soil conditions (pH < 6.0) can limit the bioavailability of P and K [46]. Adjusting soil pH to the optimal range (6.0 to 7.5) enhances nutrient solubility and uptake [17,41], which likely contributed to the observed increases in P and K concentrations. While some studies have reported decreased P content or no effect on K levels with mussel shell amendments, the present study recorded notable improvements in nutrient concentrations [27,28]. Such discrepancies may be attributed to differences in soil conditions, application rates, or shell characteristics among various studies. In contrast, the application of mussel shells did not result in statistically significant changes in total N content across treatments. This finding is consistent with other research indicating no significant differences in total nitrogen with mussel shell amendments.
Overall, the positive impact of ground mussel shells on phosphorus (P) and potassium (K) levels underscores their potential as effective soil amendments for improving nutrient availability. The enhancement of these nutrients, however, is closely linked to soil microbial activity, which is sensitive to changes in soil pH [29,47]. By raising soil pH, a more conducive environment for beneficial microorganisms is created, which, in turn, supports nutrient cycling and overall soil health. This interaction between nutrient availability and microbial dynamics emphasizes the importance of pH adjustments in optimizing soil fertility, thus making the potential reutilization of mussel shell waste a promising and sustainable resource for enhancing agricultural soils.
While a few studies have explored the potential impact of sea shells as soil amendments for different crops on a small scale [25,26], broader implementation faces challenges, particularly in scalability and availability. Shell waste is often localized to coastal areas, where mussel farming thrives, making shells more accessible and reducing transportation costs. For inland areas, however, higher logistical expenses could limit direct application. These costs may be offset, however, as mussel shells, classified as waste, already require disposal, which incurs transport and processing fees. Redirecting these costs toward agricultural use aligns with waste valorization principles, turning a disposal expense into a sustainable resource. Additionally, shells can be used directly as soil conditioners or integrated into specialized soil products, potentially enhancing nutrient delivery across diverse soil types. Exploring this alternative, along with its implications for soil condition, crop productivity, and the long-term sustainability of these enhancements, requires further research but could provide valuable insights into the practical applications of mussel shell amendments in agriculture in alignment with circular economy principles.

5. Conclusions

Mussel shells, due to their calcium carbonate content, show promise in raising soil pH and enhancing soil fertility. Our study suggests that mussel shells not only improve soil pH but also increase organic matter, available phosphorus (P), exchangeable potassium (K), and nitrogen (N), indicating their potential as a promising alternative to conventional lime. By repurposing aquaculture by-products like mussel shells for soil enhancement, this approach not only promotes sustainable agriculture but also contributes to resource conservation by reducing waste disposal and reliance on non-renewable liming materials. However, additional research, particularly comparing their performance with traditional liming materials and exploring their long-term effects, will help refine their practical application and ensure their broader utility in diverse agricultural settings.

Author Contributions

Conceptualization, A.L. and K.M.; methodology, A.L., K.M., K.G., C.A. and A.P.; validation, A.L., K.M., K.G., C.A. and A.P.; software, A.L. and K.G.; investigation, A.L., K.M., K.G. and A.P.; data curation, A.L., K.M., K.G., C.A., A.P., K.S. and D.V.; writing—original draft preparation, A.L., K.M., K.G., C.A., A.P., K.S. and D.V.; writing—review and editing, A.L., K.M., K.G., A.P., A.P., K.S. and D.V.; supervision, A.L., K.M. and K.G.; project administration, A.L., K.M. and K.G. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are contained within the article.

Acknowledgments

The authors would like to thank the Editors and the three anonymous reviewers for their insightful and constructive feedback. Their comments have significantly improved the quality and clarity of the manuscript, and we deeply appreciate the time and effort they dedicated to reviewing our work.

Conflicts of Interest

The authors declare no conflicts of interest.

Appendix A

The experimental matrix employed in the study was based on a Completely Randomized Design (CRD). The matrix outlines the combinations of factors and their levels used to evaluate the impact of mussel shell application on soil pH and nutrient availability. This design was chosen to ensure that the variability among treatments could be accurately assessed, thereby enhancing the robustness of the experimental results (Figure A1).
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Figure A1. Experimental matrix used in the study, showing the variables and levels tested.
Figure A1. Experimental matrix used in the study, showing the variables and levels tested.
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The following figures display additional diagnostic plots to support the regression analysis discussed in the main text. The normal probability (residuals) plot, residuals vs. predicted response plot, and predicted response vs. actual value plot are provided to evaluate the model’s performance and ensure the validity of the results (Figure A2, Figure A3 and Figure A4).
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Figure A2. Normal probability plot of residuals. The plots compare the actual pH measurements with the predicted values for (A) coarse scale (pH_Coarse) and (B) fine scale (pH_Fine).
Figure A2. Normal probability plot of residuals. The plots compare the actual pH measurements with the predicted values for (A) coarse scale (pH_Coarse) and (B) fine scale (pH_Fine).
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Figure A3. Residuals versus predicted response plot. Residuals are shown as a function of the predicted pH, with the blue line indicating zero residuals.
Figure A3. Residuals versus predicted response plot. Residuals are shown as a function of the predicted pH, with the blue line indicating zero residuals.
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Figure A4. Predicted response versus actual values plot. The residuals are plotted against row numbers, with the blue line representing zero residuals (perfect fit), green lines denoting ± 2 standard deviations, and red lines indicating ± 3 standard deviations.
Figure A4. Predicted response versus actual values plot. The residuals are plotted against row numbers, with the blue line representing zero residuals (perfect fit), green lines denoting ± 2 standard deviations, and red lines indicating ± 3 standard deviations.
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Figure 1. Map of the wider region and location of the sampling area.
Figure 1. Map of the wider region and location of the sampling area.
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Figure 2. pH values of experimental pots from the six different treatments of soil mixed with (A) Fine Powder of ground mussel shells (grain size < 1 mm, FP); (B) Coarse Powder of ground mussel shells (grain size 1–2 mm, CP).
Figure 2. pH values of experimental pots from the six different treatments of soil mixed with (A) Fine Powder of ground mussel shells (grain size < 1 mm, FP); (B) Coarse Powder of ground mussel shells (grain size 1–2 mm, CP).
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Figure 3. Response Surface Methodology 3D and contour plots of (A) pH combined with the Fine Powder (FP) and (B) pH combined with the Coarse Powder (CP).
Figure 3. Response Surface Methodology 3D and contour plots of (A) pH combined with the Fine Powder (FP) and (B) pH combined with the Coarse Powder (CP).
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Figure 4. Principal component plot for the different soil properties (OM: organic matter, P: available phosphorus, K: exchangeable potassium, N: total nitrogen, FP: Fine Powder, CP: Coarse Powder).
Figure 4. Principal component plot for the different soil properties (OM: organic matter, P: available phosphorus, K: exchangeable potassium, N: total nitrogen, FP: Fine Powder, CP: Coarse Powder).
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Table 1. Physicochemical properties of the soil used for the experiment.
Table 1. Physicochemical properties of the soil used for the experiment.
PropertyValue
Silt (%)26.0
Clay (%)43.1
Sand (%)30.9
pH4.26
Electrical conductivity (μS cm−1)921.1
Organic carbon (%)0.70
Organic matter (%)1.21
Total nitrogen (N) (%)0.11
Available phosphorus (P) (mg kg−1)23
Exchangeable potassium (Κ) (mg kg−1)120.9
Table 2. Physicochemical properties of the different ground mussel shell powders used for the experiment.
Table 2. Physicochemical properties of the different ground mussel shell powders used for the experiment.
PropertyValues
Fine Powder (FP)
(<1 mm)		Coarse Powder (CP)
(1–2 mm)
pH7.088.72
Calcium Carbonate content (CaCO3) (%)75.324.7
Organic carbon (%)1.60.35
Organic matter (%)2.760.61
Total nitrogen (N) (%)0.90.51
Available phosphorus (P) (mg kg−1)397.7116.2
Exchangeable potassium (Κ) (mg kg−1)137.854
Table 3. Analysis of Variance (ANOVA) for soil pH_Fine Model and pH_Coarse Model response.
Table 3. Analysis of Variance (ANOVA) for soil pH_Fine Model and pH_Coarse Model response.
pH_Fine Model
SourceDFSum of SquaresMean SquaresF Ratiop-Value
Model566.51163813.302379.1544<0.05
Error305.0416630.1681
Total3571.553300
pH_Coarse Model
SourceDFSum of SquaresMean SquaresF Ratiop-Value
Model539.91887.9838140.2710<0.05
Error301.70750.0569
Total3541.6263
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MDPI and ACS Style

Lolas, A.; Molla, K.; Georgiou, K.; Apostologamvrou, C.; Petrotou, A.; Skordas, K.; Vafidis, D. Evaluating the Liming Potential of Mytilus galloprovincialis Shell Waste on Acidic Soils. Conservation 2024, 4, 778-791. https://doi.org/10.3390/conservation4040046

AMA Style

Lolas A, Molla K, Georgiou K, Apostologamvrou C, Petrotou A, Skordas K, Vafidis D. Evaluating the Liming Potential of Mytilus galloprovincialis Shell Waste on Acidic Soils. Conservation. 2024; 4(4):778-791. https://doi.org/10.3390/conservation4040046

Chicago/Turabian Style

Lolas, Alexios, Katerina Molla, Konstantinos Georgiou, Chrysoula Apostologamvrou, Alexandra Petrotou, Konstantinos Skordas, and Dimitris Vafidis. 2024. "Evaluating the Liming Potential of Mytilus galloprovincialis Shell Waste on Acidic Soils" Conservation 4, no. 4: 778-791. https://doi.org/10.3390/conservation4040046

APA Style

Lolas, A., Molla, K., Georgiou, K., Apostologamvrou, C., Petrotou, A., Skordas, K., & Vafidis, D. (2024). Evaluating the Liming Potential of Mytilus galloprovincialis Shell Waste on Acidic Soils. Conservation, 4(4), 778-791. https://doi.org/10.3390/conservation4040046

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