*3.3. Pesticide Residue Pollutant Analysis and Medical Waste*

It is suspected that pesticide residue and medical waste are contaminating the marine waters around BCI. This conclusion is based on the GC/MS chromatogram, which identified several types of organic compounds containing acidic groups (phenol, arsenous acid, sulfurous acid), carboxylic acid (hexadecenoic, benzoic acid), halogen groups (chloridanthene, fluoranthene, blomidanthene), phosphate, cyclopentasiloxane, thiophene, silicic acid, benzo[h]quinolone, and cyclotrisiloxane [16,40,42]. These compounds are thought to be derived from pesticide residues and medical waste and then change during their stay in the aquatic environment. This assumption was confirmed by the GC/MS chromatogram [77,94,95].

The components of pesticide residue and medical waste are not presented significantly in tabular form. The abundance of chromatogram peaks is due to the similarity or suitability of components with references in the tool library, which is less than 85% [12,26,96]. Determination of a component based on the GS/MS measurement is considered valid if it has a similarity level or quality of 80%, as was completed for the hydrocarbon and PAH components [14,17,42,48,97]. Ideally, for the analysis of pesticide residue and medical waste in samples obtained from marine ecosystems, such as from fish, sponge, seawater, and sediment, the preparation of these samples should be carried out using a combination of pyrolysis-GC/MS instruments [46,48,98,99].

## *3.4. Heavy Metal Pollutant Analysis*

Many heavy metal pollutants are thought to enter the marine ecosystem. However, only Lead (Pb) and Copper (Cu) ions were identified in this research. Observations made in the Makassar City MTA area concluded that these two types of pollutants are the most significant components of pollution in marine areas, especially around BCI in the Spermonde Islands group [11,13,36,100].

Based on the quality standard according to KLH RI Num. 51/2004, the average concentration of the heavy metals Pb+2 and Cu+2 in seawater should be a maximum of 0.05 mg/L [4,10,33,62]. Comparing the concentrations identified in the results (Table 7) with the seawater quality standards showed that the pollutant concentrations of Pb+2 and Cu+2 around BCI were 20 times and 25 times higher than the required quality standards, respectively [44,48,62,100]. According to the Director General of BPOM RI No. 03725/B/SK/VII/89, the maximum threshold value of heavy metal contamination in fish for pollutants Pb+2 and Cu+2 = 0.008 μg/g [33,55,82,101]


**Table 7.** Heavy metal pollutant (HM) concentration analysis.

The data on the average concentrations of the two heavy metal pollutants (Table 7) show that exposure to Pb+2 and Cu+2 is still below the threshold value. However, using the Australian and New Zealand Environment and Conservation Council (ANZECC) standard, with a smaller tolerance value than the maximum threshold, it was concluded that the two pollutants found in fish around BCI exceeded the standard [10,55,76,102,103]. Based on the data, Table 7 shows that all types of samples (fish, sponges, seawater, and sediments) obtained in the waters around BCI have exceeded the maximum threshold value specified [4,10,48,104]. This is understandable and quite rational because consumption patterns, activities, and dynamics in each type of marine fish vary greatly. Fish samples were obtained for analysis from different stations (Table 2). The type of fish sampled at ST 1 (Chrysiptera unimaculata) differed from the fish samples from ST 2 and ST 3 [62,105,106].

#### **4. Discussion**

Physical observation of the waters around BCI did not find plastic waste, media waste, or oil spills. The physical characteristics of Barrang Caddi waters (EC, TDS, pH, and temperature) and other parameters (Table 1) were similar to those of surrounding marine waters [107]. It is known that the contaminants in the GTP group are invisible. Demographically, the distance between BCI and Makassar City is ±11.5 km, the land area is ±45,000 m2, and the population is ±3000 people (612 families) (Figure 1). The residents generally make their livelihoods through the fishing industry, and some have vegetable gardens and undergo traditional household processing, generally burning [108,109]. Such conditions have ecological relationships and the potential to contribute to exposure to GTP contaminants [110].

The morphology of the fish and sponges differed at each station (Table 2). In marine ecosystems, fish interact with seawater as a growth medium throughout their lives, and the dominant sponges interact more with sediment (Figures 2–5). These factors cause differences in life patterns, the dynamics that occur between types of fish and sponges, and differences in the nutritional patterns of the two types of marine biota (fish and sponges) in terms of their growth media, their level of preference for types of nutrients, and their limit of tolerance to GTP contaminants [111,112].

The results for the total abundance of MP for each type of sample analyzed (Figures 2 and 3) showed that the waters around BCI are exposed to MP pollutants [18]. The type of MP contaminant contained in each sample type was analyzed further in terms of the density (film, fiber, fragment). The suspected types of MP based on polymer structures were distinguished by measurement and analysis, using the difference spectrum seen on the FTIR chromatogram (Figures 4 and 5) [38,77]. These observations show that the marine ecosystem around BCI waters is exposed to almost all types of MP contaminants [34,113]. The dominant MP found in all samples was the mild MP group (PE, PP, PS), followed by the heavy group (PA and PC), while few of the PVC and ABS types were found (Table 3) [26,42]. The data illustrate that the dominant source of MP contaminants is community activities, including industry, services, and household activities [87]. This type of MP is widely used in packaging applications, such as in the manufacture of plastic bags, clothes, ropes, coloring, and recycling containers, as well as various types of plastic caps, bottles, disposable tableware, and optical discs (CDs). Almost all of the uses of this type of MP are part of the daily activities of society and industry [114,115].

The other GTP contaminants analyzed were hydrocarbon components, especially PAHs. Research was carried out on all types of samples from three different stations (Tables 4–6), and eight types of PAH were identified. In terms of types of low-toxic PAH, the NL type was identified in all samples. NL is a simple aromatic hydrocarbon [9,38,116]. Naphthalene-based products, such as camphor, are thought to come from household activities, for example, in products used to eradicate insects and absorb odors in bathroom toilets. Another source can be the distillation of coal tar. The nature of NL is volatile and carcinogenic [14,117].

Pyrene is a second order PAH that was identified in several samples. PN is a group of highly toxic and carcinogenic PAHs. The presence of PR in the sample is thought to have come from the transportation activities of petroleum carriers. This assumption was reinforced by the identification of the PAH type AZ, as the PAH type is a component of petroleum as are some of its derivative products, including those from coal processing [9,84,118]. This allegation is quite reasonable, because BCI operates three ports: a container port, a passenger port, and a fish-landing port. Other PAHs, such as PT, PH, and BZ, are derivative products resulting from chemical reactions, such as oxidation reactions that produce these derivatives or community waste burning activities [71,119].

Pesticide residues and medical waste are strongly suspected to be pollutants in the marine ecosystem around BCI. This assumption is based on GC/MS chromatogram peaks of varying abundances and the recorded GC/MS chromatogram peaks identified with PR and MW components and observed in the PAH chromatogram data (Tables 4–6), where the peak numbers not listed in the table are the peaks of the PR component or residual MW [73,109,116]. This assumption is based on the fact that two hospitals operate around the coast of Makassar City, which is adjacent to BCI [51,120]. The presence of the pollutant types PR and MW in samples of fish, seawater, sponges, and sediments around the marine waters of BCI could also have come from the activities of the people who inhabit BCI or be due to biological activities, where these pollutants undergo dynamic activities and eventually empty into the sea [24,55,96,110].

Heavy metal (HM) pollutants, especially Pb+2 and Cu+2, were identified in all of the samples obtained from the three different stations (Table 7). These results indicate that the concentrations are within the tolerable concentration limits for marine biota and are not dangerous according to Indonesian KLH standards, but they are in the worrying category based on ANZECC standards [12,62]. Pb+2 and Cu+2 pollutants in marine ecosystems around BCI are also thought to be due to natural and anthropogenic activities [20,121,122].

The concentration of all types of GTP identified in the waters around BCI is at alert status, not only in terms of the quality and sustainability of the marine ecosystem around BCI but also for the people who inhabit the island and the tourists visiting the island. In addition, the survival of sponges is important, as they are known to have primary and secondary metabolic contents that are used as raw materials for medicinal products, food concentrates, and beauty products [62,83,111,123].

It is estimated that exposure to contaminants from the GTP group around BCI will increase in the future due to the island's status as part of the Marine Tourism Area (MTA), meaning that it is visited by many tourists, which is seen as a potential factor contributing to the pollutant component, especially the pollutant types MP and PAH [65,69,80]. BCI is adjacent to the city of Makassar, which has a beach length of ± 7.5 km. Anthropogenic sources of pollutants are thought to heavily contribute to this sector. Along the coast, there are hotels, hospitals, industrial operations, culinary areas, and residential housing [1,11,40]. The area is very densely populated, and community activities occur every day for almost 24 h per day [7,10,80]. This situation is thought to be the main factor causing exposure to MP pollutants of the MW type. The vicinity of BCI is also adjacent to the Soekarno-Hatta Port, a fish-landing port. Thus, there are many transportation activities for various types of ships. This significantly contributes to exposure to pollutants, especially pollutants of the PAH, HM, and MP types [13,46,101].

We recommend that the Makassar City MTA manager should use this data as material for consideration in MTA operations, so that the managed marine tourism does not cause increases in pollutants from the GTP category [3,47]. It is expected that the tourist area could be improved by increasing the population of marine biota, especially sponges, through the transplant method, as sponges are known as biota with functions, such as biodegradation, bio-absorption, and the bioremediation of several types of pollutants including PAHs, microplastics, and heavy metals [20,121]. Sponges can be used as bioindicators and for the biomonitoring of PAH and HM contamination [44,73,122]. Efforts should be made along the shoreline of BCI, and it is recommended that plants that have a biofilter function against pollutants, such as mangroves, should be planted [124]. Makassar City MTA managers are also advised to carry out socialization, education, and advocacy with the community to make them aware of the effects of waste, so that their household waste can be appropriately managed and not enter sea waters.

#### **5. Conclusions**

This article reviewed microplastic pollutants, PAHs, pesticide residue, heavy metals, and medical waste, which are known as global trending pollutants (GTP) and are present in marine ecosystems around BCI's MTA waters. The average total MP abundance was found to be 5.47 units/m3 in seawater samples, 7.03 units/m3 in fish, 8.18 units/m3 in sediment samples, and 8.32 units/m<sup>3</sup> in sponges. Seven types of MP were identified in the BCI aquatic ecosystem, dominated by the mild categories of MP, PE, PP, and PS, followed by PA and PC. The marine ecosystem around BCI was found to be contaminated with PAH-type pollutants, especially the NL type, which was found in all samples, followed by PN and AZ. BCI waters are also suspected of being exposed to pesticide residue and medical waste. The heavy metal pollutants Pb+2 and Cu+2 were also identified in the marine waters around BCI, especially in fish and seawater samples. The average concentrations of Pb+2 and Cu+2 in seawater were 0.164 ± 0.0001 mg/L and 0.293 ± 0.0007 mg/L, while the average concentrations of these two types of heavy metal pollutants were 1.811 ± 0.0002 μg/g and 4.372 ± 0.0003 μg/g, respectively.

The five types of pollutants identified in the marine ecosystem around BCI illustrate that this MTA is not conducive to being a recommended marine tourism destination. It is estimated that the concentrations of these pollutants will increase, given the status of BCI as one of the islands in the MTA area. If the BCI is maintained as a marine tourism area, it is feared that its ecosystem will enter an ecological hazard state, which will have a chain effect, not only on the aquatic ecosystem around the BCI but also on the sponge populations and fish, leaving them unfit for consumption and subsequently causing health problems for the community.

**Author Contributions:** Conceptualization, I.M., E.S., E.S.K., A.A. and K.N.; methodology, I.M., H.H., R.A. and A.A.; software, I.M. and A.S.; validation, I.M., S.S. and B.H.I.; formal analysis, I.M., F.R. and E.H.; investigations, I.M., R.A. and I.S.S.; resources, I.M., G.S.S. and R.A.; data curation, E.S.; writing—original draft preparation, I.M., I.S.S. and K.N.; writing—review and editing, K.N., E.S.K. and F.R.; visualization, H.H. and A.S.; supervision, S.S., I.S.S. and E.H.; project administration, I.M., A.A.; funding acquisition, I.M., B.H.I. and G.S.S. All authors have read and agreed to the published version of the manuscript.

**Funding:** This research received external funding from the "Ministry of Research, Technology and Higher Education/National Research and Technology Agency, who granted funds in 2021 under the applied research scheme, according to Master Contract numbers 315/E4.1/AK.04.PT/2021" and 1868/E4/AK.04/2021, dated 7 June 2021". Support was also received from Fajar University under the Work Implementation Order, contract Number: 29/AI/LPPM-UNIFA/IV/2021, dated 19 May 2021.

**Institutional Review Board Statement:** Not applicable.

**Informed Consent Statement:** Not applicable.

**Data Availability Statement:** Data sharing is not applicable to this article.

**Acknowledgments:** We thank Hasanuddin Biochemistry Laboratory, Department of Chemistry for their support through the use of their facilities. Makassar Plantation Product Industry Center (BBIHP) is a partner for this research. We acknowledge the research collaboration with the Research Institute for Coastal Aquaculture and Fisheries Extension, Maros, and BRIN as parties, including several individual partners from several campuses.

**Conflicts of Interest:** The authors declare no conflict of interest.
