3.1. Heavy Metal Levels
Table 11 and
Table 12 show the heavy metal concentration detected in the San Giuliano and Camastra reservoir shore surface samples. The tables also show the limit of quantification (LoQ) and the threshold concentration defined in [
66], taken as the background value in the determination of some of the indices. It should be specified that the analyses carried out covered a more significant number of pollutants than those shown in
Table 11 and
Table 12; in any case, only the most important ones used to define the pollution indices are reported in this study.
The comparison between the values detected by the laboratory analysis and the legal limits shows that the concentration of heavy metals in shore surface sediments is always below the specific regulatory threshold. This condition does not occur for the samples named SG_S5 and SG_S6, where the regulatory limit for the heavy metal Arsenic is exceeded, and for the specimens named C_S3, C_S4, C_S8, C_S9, and C_S11, concerning the concentration detected for Co.
For the sediments of the San Giuliano reservoir, it is noted that the concentrations of heavy metals are ordered according to the following pattern: Fe > V > Zn > Cr > Ni > Cu > Pb > As > Co > Be > Sb > Tl. In contrast, the pollutants’ values found in the Camastra reservoir deposits present the following sequence: Fe > Zn > V > Cr > Ni > Cu > Co > Pb > As > Be > Sb > Tl. Thus, many similarities are found between the heavy metal concentrations at the two reservoirs, with overall overlapping values, except for some metals, such as Zn, Cu, Co, and As, the first three richer at the Camastra reservoir and the fourth more abundant in the sediments of the San Giuliano reservoir.
Analysis of average values shows no exceedance of threshold values set by national regulations. Sediments from the Camastra reservoir exhibit higher average values of pollutants (about 40–50%) than materials taken from the banks of the San Giuliano reservoir, except for Arsenic, with, on average, a higher concentration at the latter reservoir.
Figure 4 shows that the contaminants’ levels for the shore surface sediments of the San Giuliano reservoir (a) do not depend on the location of the sampling site compared to the dam, as the highest values of the different heavy metals are shown in the samples named SG_S1, SG_S5, and SG_S11, both in the upstream and in the downstream areas. Even the SG_S8 sample shows peaks, especially for Cr, Ni, V, and Zn. Relative to contaminant concentrations for the Camastra reservoir (b) shore surface sediments, however, it is found that heavy metals are abundant in the central areas of both the reservoir banks (sediments C_S3, C_S9, and C_S11). They are more abundant overall in the upstream areas of the reservoir banks than in the downstream areas, where values are always lower.
For both reservoirs, it is highlighted that the pollutants’ shore surface distributions show peak values for more than one heavy metal. Specifically, by analyzing the trends at the San Giuliano reservoir, we found that the shore surface samples SG_S1, SG_S5, SG_S8, and SG_S11 show peak concentrations that are not detected in other samples, even those that are geographically close. In addition, the substantial increase in As in sample SG_S5 is related to the increase in other heavy metals (V, Ni, Cu, Pb, Co), probably arising from the same source.
By mirror reasoning, the same behavior is also found in the pollutant shore surface distributions of the Camastra sediments, where some surface samples show what was also highlighted for the San Giuliano reservoir sediments. For example, sample C_S3, which is characterized by a Co concentration above the regulatory threshold, also shows peaks of concentration for other heavy metals (Cr, Cu, Ni, Pb, Tl, V, Zn), so that similar conclusions to those above are reached.
As shown in Martellotta et al., 2024 [
67], the granulometric composition of the San Giuliano and Camastra reservoir sediments differs depending on the area from which the samples came. In fact, for both reservoirs, there is a predominance of the sandy component for sediments sampled near the dam and, on the contrary, a greater relevance of the silt-clay component in those coming from the upstream areas. The analyses relating to the organic component show that the organic matter content is greater for surface sediments from the Camastra reservoir than for those sampled from the banks of the San Giuliano reservoir. All sediments, however, have an organic matter content of less than 2%, so it can be considered negligible.
The samples SG_S5, SG_S6, SG_S8, and SG_S11 show the highest heavy metal content, corresponding to a predominant silt-clay grain size component and their position in the upstream areas of the reservoir. Regarding the organic matter content, sediment heavy metal concentration does not directly correlate with the measured values, except for sample SG_S5, for which the higher organic matter content corresponds to the higher heavy metal concentration.
Also, for the Camastra reservoir sediments, the most contaminated samples are located in the upstream areas, near the inlets of the Inferno and Camastra rivers, where the sediments are predominantly characterized by a clayey-silt matrix. In contrast to the San Giuliano sediments, for those in the Camastra, the sediments with the highest contaminant content are also those with the highest organic matter content.
Finally, it is noted that the variation in heavy metal content between all the samples is a direct consequence of the composition of the grain sizes of all the sediments analyzed within the same basin.
A comparison of the heavy metal contamination data in the sediments of the Camastra and the San Giuliano reservoirs with the data found for other reservoirs in the literature reveals that the Ni, Cu, and Zn concentrations are in line with the published parameters, in contrast to Pb, whose values found for the reservoirs examined are always significantly lower [
68,
69]. It has similar values to those determined for the surface sediments of Lake Taihu in China, except for samples SG_S5 and SG_S6 [
70]. For Cr, on the other hand, the concentrations in the Camastra and San Giuliano sediments are always significantly lower than the corresponding values found for the Taihu Lake sediments, and are in line with those identified for Lake Symsar in Poland [
71]. The extent of heavy metal contamination in the sediments of the investigated reservoirs is, therefore, not much more serious than in other similar studies.
3.2. Pollution Indices for Sediment Properties Evaluation
The sediment pollution evaluation, essential to defining its compatibility for reuse, was carried out by determining nine indices, which are made explicit in
Section 2.4. Each of the indices was then compared with its respective threshold values to identify whether the sediments were polluted or not.
Table 13 shows the pollution indices determined from the heavy metal shore surface distribution detected by sediment analysis of the San Giuliano reservoir. The shore surface sediments show a condition of absence of pollution or traces concerning most of the indices detected, although not for all. Three pollution indices (
PN,
PIvector, and
PIN) show the presence of contaminants or a low degree of pollution, with some differences. Nemerow’s pollution index indicates that only sample SG_S5 is characterized by a non-polluted condition, but at the limit (“warning limit”). On the other hand, the
PIvector and
PIN indices report moderate pollutant content for only samples SG_S5 and SG_S6 (more evident and relevant for the former, less so for the latter). These sediment samples are the same ones for which As is reported to exceed the threshold value established by [
31], thus highlighting how this heavy metal is the main factor responsible for the moderate pollution degree detected. Concerning the average values of all indices, however, the reservoir sediments appear not to be contaminated overall.
Table 14 shows the values of the indices calculated for the Camastra reservoir shore surface sediments. It is noted that, for seven of the ten indices determined, the sediments show no polluted condition, identified as “clean” or “unpolluted,” and contamination can be defined as “low” or “absent.” The
PIvector and
PIN indices, on the other hand, show that the Camastra sediments are characterized by a low content, or traces, of pollution, but only for the samples named C_S3, C_S4, C_S8, C_S9, and C_S11. Those are the specimens where Co exceeds the limit values; thus, it can be inferred that this heavy metal is responsible for the slight pollution condition identified. Moreover, the average value for each index is always below the thresholds above which sediments can be considered contaminated, even slightly.
For both reservoirs, the highest values of the indices are associated with the Potential Ecological Risk (
RI) index and the Background Enrichment Factor (
PIN), even for the samples where the threshold concentration values are exceeded (
Figure 5).
The values of the EF and MEC indices, which denote the possible pollution linked to anthropogenic activities, show that the exceedance found for As in the San Giuliano sediments and Co in the Camastra sediments is attributable neither to agronomic practices nor to the possible existence of industries but to the nature of the analyzed materials.
The spatial analysis of pollution indices as a function of the distance from the dam shows that the highest values are recorded for the sediments sampled at the central areas of both reservoirs’ banks, with no pollution in both upstream and downstream areas of the banks, where the pollution indices tend to be almost similar.
Examined indices for surface coastal sediments of the Camastra and the San Giuliano reservoirs are similar to those examined in other studies, both for sediments from reservoirs and for river sediments [
38,
42,
52,
68,
69,
70].
3.3. Multivariate Statistical Evaluation
3.3.1. Cluster Analysis
Cluster analysis (CA) was carried out to assess any similarities between sediments sampled in different areas of the reservoirs (spatial variability). For both the San Giuliano and the Camastra lakes, the assessments performed returned a dendrogram (
Figure 6) in which all sampling sites, twelve for the San Giuliano and thirteen for the Camastra, were clustered into two statistically significant clusters, in both cases with a threshold of 60% (Height).
For the San Giuliano, the two clusters consist of sites SG_S2, SG_S3, SG_S4, SG_S7, and SG_S12, and sites SG_S1, SG_S5, SG_S6, SG_S8, SG_S9, SG_S10, and SG_S11, respectively. The two clusters obtained are heterogeneous, containing both upstream and downstream samples belonging to both reservoir banks, indicating that the pollution content is relatively uniform for the entire reservoir and that no peculiar elements significantly influence the pollutant content in sediments. Therefore, similar anthropogenic factors influence the heavy metal content in all samples. The main difference is in the heavy metal pollution content, where the cluster 1 group samples are characterized by a slight heavy metal concentration around the sampling sites, as opposed to the higher contamination level at the sampling sites belonging to cluster 2.
Regarding the Camastra reservoir, the two clusters identified reflect the spatial distribution of sampling sites. The cluster 1 group samples C_S3, C_S4, C_S8, C_S9, C_S10, and C_S11 all belong to the central area of the reservoir; cluster 2, on the other hand, contains samples C_S1, C_S2, C_S5, C_S6, C_S12, and C_S13, located in the downstream and upstream zones. The different pollution levels of specimens, whose probable sources will be discussed in the next section, therefore depend on the location of the sampling sites. The main difference between the areas related to the identified clusters lies in the presence of mobility infrastructure (roads, bridges, etc.) in the upstream and downstream areas, although with limited traffic concentration, in contrast to the central area.
3.3.2. Correlation Matrix
Table 15 and
Table 16 show the correlation matrices of the heavy metals detected in the San Giuliano and Camastra sediments to determine the common pollution sources in the samples. For heavy metals whose samples have a normal distribution, the values of Pearson’s correlation coefficient are given; if the data distribution does not follow the Gaussian curve, the table contains the value of Kendall’s τ coefficient.
For the San Giuliano reservoir, there is a significant positive correlation between some of the heavy metals studied. Pearson’s coefficient values are close to unity, with a p-value of less than 0.01, and are found for several parameters. Be is significantly correlated with Cr, Cu, V, and Zn; Co shows a significant relationship with Ni and Pb. In addition, a relevant correlation is also recorded between Cr, Cu, Ni, V, and Zn, indicating that these elements probably originated from the same source. Regarding the correlation between heavy metals whose data do not follow a normal distribution, Kendall’s τ coefficient values show an important significance degree between As and Sb, with a p-value < 0.01.
For all other heavy metals, the correlations are negative or, at any rate, insignificant, indicating relatively complex pollution sources.
3.4. Ecological Risk Assessment
To assess the potential ecological risk associated with the shore surface distribution of pollutants in sediments sampled at the Camastra and San Giuliano lakes’ banks, the RI index, described in
Section 2.4.9, was evaluated [
72].
Table 9 and
Table 10 show that the contaminant medium values in the investigated shore surface sediments for the calculation of this index (As, Cr, Cu, Ni, Pb, Zn) are, for both reservoirs, consistently lower than the concentration threshold values set by current Italian standards. In addition, values are higher than the toxicity response in the latter case, except for the As value for the Camastra reservoir. Specifically, for the Camastra reservoir, the values of Cr, Cu, Ni, Pb, and Zn are about 30 times, 6 times, 9 times, 3 times, and 42 times higher than the related toxicity response value, respectively; on the contrary, the concentration of As is 70% of the value reported in
Table 7. Regarding the San Giuliano reservoir, however, it is found that the concentrations of As, Cr, Cu, Ni, Pb, and Zn are about 1.5 times, 19 times, 3 times, 6.5 times, 2 times, and 22 times higher than the related toxicity response value, indicating that these heavy metals could partly come from contamination sources outside the reservoir [
73].
Figure 5 shows, among all indices, that
RI ranges from a minimum of 4.08 to a maximum of 33.49 for the San Giuliano reservoir shore surface sediments and from a minimum of 7.05 to a maximum of 15.69 for the Camastra reservoir coastal shore surface sediments. Considering the categories for
RI value shown in
Table 8, all samples are classified with “low” pollution risk. The distribution of
RI values for the San Giuliano reservoir (
Figure 5a) almost overlaps with the
PIN index and the Camastra reservoir (
Figure 5b). Furthermore, for both reservoirs, it is shown that the potential ecological risk of the upstream areas is, on average, higher than that of the downstream areas. Since the potential ecological risk index defines the level of potential risk associated with the presence of pollutants in a certain environment, this study’s results indicate that the areas more susceptible to pollution risk are, for both reservoirs, those upstream, whose lithogenic composition is such that the sediments are potentially less employable.
Finally, for the San Giuliano reservoir, the RI index appears to be highest for samples SG_S5 and SG_S6; in contrast, sediments sampled at the Camastra reservoir banks take the highest value at sites C_S3, C_S4, C_S8, and C_S9. Since the sites mentioned before are the same for which exceedances occurred for As in the San Giuliano sediments and Co in the Camastra sediments, respectively, it is evident that the peak RI value shown in the trends is closely related to and influenced by these heavy metals.
3.5. Metal Pollution Sources
The analyses carried out up to this point, especially the statistical evaluations, were focused on assessing the shore distribution of pollutants for the sampled at surface sediments and, once this was defined, evaluating the possible sources influencing the concentration of heavy metals, according to the procedure in Duodu et al., 2016 [
37]. The shore surface sediments of the two reservoirs considered, with different geology, lithology, land use, anthropization, and, more generally, characteristics, show significantly different parameters, facilitating the assessments carried out in this section.
Regarding the exceedance of the concentration threshold value for As at the San Giuliano reservoir, the two shore surface samples (SG_S5 and SG_S6) were spatially close and grouped in the same cluster, so the pollution sources are multiple. The analysis of the geology of the area, both the San Giuliano basin and the catchment areas of the lateral tributaries, shows the predominance of alluvial deposits that contain organic substance, determining the concentration of metals and results in the accumulation of arsenic in the sediments, where it reaches due to the transport by the tributary streams. In addition, the peat that characterizes the surface layer of the soil typically shows a conspicuous As content. An additional factor influencing the higher value of this heavy metal in the shore surface sediments is algal organic matter reaching the lake environment, also introduced by the lateral, temporary, and permanent tributaries. The influence of the organic matter is confirmed by the value above the thresholds of some pollution indices and by what is shown in
Table 13 and
Table 14, since its accumulation even increases other metals (in the present case, antimony). In addition, further As sources are the sedimentary rocks, where it is usually significant, and the reducing environment that characterizes the upstream area of the lake, as evidenced by the specimen’s dark grey colour; these avoid the transition from oxidation state V to oxidation state III, are much more soluble and, therefore, are more prone to leaching.
Concerning the regulatory limits exceedance for Co in the Camastra shore surface sediments, the primary source of this heavy metal is the ultra-basic magmatic rocks, which concentrate iron–magnesium minerals, in which cobalt tends to accumulate, prevalent within the watershed of the Inferno and Camastra rivers, and their lateral tributaries, which feed the reservoir. In addition, the geological composition of the upstream areas even points to the presence of sedimentary rocks, in which cobalt is also concentrated, as well as in soil with organic matter.
In both reservoirs, Pearson’s correlation test shows a significant correlation between V and Cr, suggesting that the contamination of coastal shore surface sediments is due to anthropogenic input, related to leached ground discharges from rainfall falling into the Camastra reservoir and deriving from the lateral tributaries’ contribution. Ni and Zn also have a significant correlation for both reservoirs, indicating phenomena of diesel and lubricating oil combustion and tire and brake abrasion. This is explained by the accessibility of the reservoir areas by motor vehicles, which can arrive undisturbed within a few meters of the areas where the samples were taken. The further correlation found for both parameters with Cu denotes the presence of iron structures, e.g., the management and regulation organs of the dams, treated with antifouling paints. In addition, the significant correlation between As and Sb for the San Giuliano reservoir suggests a common pollutant source from the mining and smelting of antimony ores.
Finally, the low values found for the EF and MEC indices indicate that the coastal distribution of pollutants is not associated with the presence of industries, which cannot be detected in the areas close to both reservoirs. For this reason, we can assume that the values found relate to the type of rocks that characterize the areas linked to lakes and lithogenic sources.
To improve the sediment quality and limit coastal pollution, various initiatives could be started. In this sense, the improvement could take place through three main actions: the removal of sediment and recycling, the admission of unpolluted water, and the limitation of watershed erosion.