4.1. Deoxygenation and Reaeration Rates
Maintaining the water quality upstream of the Citarum River is crucial for maintaining the downstream water quality. The increasing population and the development of areas around the river have resulted in changes in human activities that impact pollution. Pollutants in the upstream of the Citarum River result from anthropogenic sources such as agriculture, households, sanitation, industry, livestock manure, and garbage. Pollution that exceeds the river’s capacity results in the deterioration of self-purification services, which impacts humans directly through the global sanitation crisis. Pollution problems in upstream rivers have a widespread impact on humans because pollutants are transported throughout the river network [
36].
The deoxygenation was calculated using Thomas’s slope method with water that was incubated for ten days. Ten days of DO measurement data for each sample point was graphed to obtain the DO loss curve over time.
Figure 2 shows the graph of the daily accumulation of DO loss for the Cihawuk and Majalaya water samples. Considering the high concentration of the initial DO concentration, the accumulated DO uptake in the rural water sample appears to be lower than in the urban sample. DO loss is an indicator of organic pollutants, as it measures the decrease in the amount of oxygen needed by microorganisms during the decomposition of organic matter [
22]. This situation suggests that the self-purification process is still ongoing. In qualitative terms, the curve also indicates a slow deoxygenation rate. Based on the observations from
Figure 2, it is evident that the Majalaya segment exhibits the highest deoxygenation rate, whereas the Cihawuk segment shows the slowest rate. Despite the low curve of accumulated oxygen usage in the Cihawuk segment, this may be attributed to the presence of a high organic matter content, indicating that the self-purification process has not yet reached an almost complete stage [
37]. The consumption of dissolved oxygen (DO) continued beyond the 10th day due to the presence of the nitrogenous oxygen demand process (N-BOD) [
38]. The substrate is assimilated by bacteria under aerobic conditions during the first phase of the BOD process, and a large amount of the substrate is transformed into biomass.
The deoxygenation rate in the rural area was lower than in the urban area. The standard deoxygenation rate for surface water is 0.10–0. 23 per day [
39]. The water from the Majalaya area is thus closer to typical deoxygenation conditions than the water from Cihawuk. Majalaya has a high deoxygenation value, which can occur due to the activity of decomposition microorganisms, which takes place quickly even though the level of pollution is high. Meanwhile, at Cihawuk, the deoxygenation rate is not as high as it is at Majalaya. This indicates that the microbial activity in decomposing organic matter is relatively sluggish. The lower value can be attributed to suboptimal microorganisms, which lead to a less efficient decomposition of the organic matter that is present in the river water [
21]. However, both are still below the standard deoxygenation rate for surface water. Other research has suggested that the deoxygenation rates in urban rivers in Indonesia are particularly low [
22].
The Cihawuk and Majalaya segments of the Citarum River are characterized by high levels of organic matter, measured as the BOD, COD, and TOM (
Table 1). The BOD and TOM levels in the Majalaya segment are higher than in Cihawuk. The BOD levels of both areas exceed the national quality standard [
35], indicating that the river is polluted. The high BOD and TOM levels in the urban area are due to organic waste from settlements, agriculture, and industry. The high BOD concentration in the urban area indicates that the organic waste is easily decomposed. Meanwhile, the Cihawuk segment of the river has a higher COD concentration than in Majalaya. The COD is the consumption of oxygen by the organic matter that is difficult to decompose. The highest COD concentration was found in the Cihawuk segment at 52.26 mg/L (
Table 1). This COD concentration exceeds the quality standard [
35]. The high concentration of COD in the rural area is due to agricultural waste and run-off (fertilizers and pesticides) that is difficult to decompose, requiring more oxygen [
40].
The concentration of oxygen required to decompose all organic matter is called the ultimate BOD (La). The ultimate BOD is derived using Thomas’s slope method. The maximum ultimate BOD values in Cihawuk and Majalaya were found to be 303.11 mg/L and 204.7 mg/L, respectively. The ultimate BOD was higher in the rural area than in the urban area. The results indicate that the Cihawuk segment has greater concentrations of both decomposed and undecomposed organic matter, and here, the river needs more oxygen to decompose the organic matter. The decomposition of organic matter in water bodies occurs in several stages, moving towards equilibrium in the aquatic ecosystem. The decomposition process of aquatic organic matter has two stages, which are carbonaceous and nitrogenous oxidation [
41]. Under aerobic conditions, the biochemical oxidation of organic pollutants produces products from bacterial action, which forms enzyme intermediates. Organic matter is stabilized by an oxidation–reduction process whereby organic matter is oxidized (as an electron donor), while dissolved oxygen is reduced (as an electron acceptor) [
42]. The process of decomposition of organic matter, namely the oxidation of carbonaceous and nitrogenous organic matter. Degradation and remediation microorganisms with only 8 mg of CH
2O can fully consume oxygen in one liter of saturated water at 25 °C [
41,
43]. Carbonaceous organic matter will be oxidized to carbon dioxide and water together with a small amount of humus with the help of aerobic heterotroph bacteria [
43]. Carbonaceous matter can be lost or added due to factors such as scouring, sedimentation, flocculation, and volatilization. Nitrogenous oxidation process is related to the conversion of ammonia to nitrite and the conversion of nitrite to nitrate, which is known as the nitrification process [
44]. The microorganisms involved in this process are a type of chemoautotroph bacteria, and the fact that nitrifying bacteria have a slower growth rate compared to heterotrophic bacteria means that the nitrification process takes longer [
45].
A high concentration of organic matter will result in a high deoxygenation rate. The problem is that the upstream of the Citarum River has high concentrations of organic matter but a low deoxygenation rate. A low deoxygenation rate indicates a slow stabilization rate, resulting in a high ultimate BOD. The deoxygenation rate measures the activity of microorganisms using oxygen to degrade different organic substances. A low deoxygenation rate indicates that the water is in an unhealthy condition because the self-purification process is obstructed [
23]. This condition may be affected by toxic or chemical compounds, which inhibit the degradation process carried out by the microorganisms in the river; these compounds may include pesticides, phenols, surfactants, heavy metals, persistent organic compounds, etc. These wastes are persistent substances that are decomposed in natural water conditions, and so they continue to accumulate in water bodies. Ultimately, the growth and performance of decomposer microorganisms is disrupted, and the self-purification process is inhibited [
22].
The reaeration rate was found to be higher in the rural area than in the urban area. The reaeration rate in the Cihawuk segment is influenced by the topography and hydrogeometry of the river, which supports turbulence, wind, and low temperatures. In streams, turbulence from the wind shear at the water’s surface yields a shallower effective mixing depth and lower gas transfer rates [
46,
47,
48]. Meanwhile, the Majalaya segment is influenced by temperature and discharge. The topography of the Majalaya segment is dominated by residential and industrial areas, so the hydrogeometry of the river is insufficient to affect water turbulence. The reaeration process plays a vital role in the self-purification process because the decomposition of organic matter requires sufficient oxygen. When oxygen is lacking, the decomposition process is not optimal and can even produce toxins due to anaerobic processes.
The local characteristics of a river have a great influence on its self-purification mechanism. The morphological shape of a river and its velocity influence its self-discharge value. In our case, the Cihawuk segment is deeper than the Majalaya segment. Depth affects reaeration because it decreases transparency; this means that the reaeration process cannot work optimally. Decreased transparency reduces the amount of oxygen that can be transferred from the water surface to the total water volume, and thus reduces the efficiency of natural atmospheric reaeration [
49]. The velocity and discharge are also influenced by the river geometry. In summary, the hydrogeometry of a river can affect self-purification processes, especially reaeration.
Overall, the self-purification processes in rural and urban areas upstream of the Citarum River basin are not significantly different. This is because the segments of the river in these two areas are still in the same upstream stream, so their characteristics are similar. However, in the rural area, the self-purification process of deoxygenation is slower, even with sufficient oxygen availability, due to the type of organic matter present in the river. Moreover, each segment’s deoxygenation and reaeration processes are significantly different; both processes have different regulating factors and final results.
The studies conducted by Yustiani [
20,
21,
22,
23] in the tributary Citarum River reported deoxygenation rates in varying ranges during different seasons. In the Citepus River, the deoxygenation rates were found to be relatively low during the dry season, ranging from 0.06 to 0.48 per day [
20]. However, during the rainy season, the deoxygenation rates in the same river increased significantly, ranging from 0.095 to 0.917 per day [
21]. Similarly, in the Cikapundung River, the deoxygenation rates were generally low, ranging from 0.001 to 0.370 per day [
22]. In the Cicadas River, the deoxygenation rates also remained relatively low, ranging from 0.010 to 0.170 per day [
23]. Overall, the studies consistently show that the deoxygenation rates in these rivers are relatively low, regardless of the river and season.
In the past, studies on the deoxygenation of the Citarum River consistently reported low dissolved oxygen levels, indicating significant impairments in its self-purification capacity. These findings are alarming and highlight the detrimental impact of pollution and anthropogenic activities on the river’s ecological health. However, the current research on deoxygenation and reaeration in the Citarum River continues to reveal similarly low dissolved oxygen concentrations, despite efforts to address water quality issues. This recurring pattern underscores the persistent challenges faced by this critical waterway in maintaining adequate oxygen levels that are necessary for sustaining aquatic life and natural self-purification processes. These findings highlight the importance of monitoring and managing water quality to maintain sufficient oxygen levels in these aquatic ecosystems and protect the well-being of the organisms relying on them. The parallel findings of low deoxygenation and reaeration rates in recent studies raise important questions about the effectiveness of the current mitigation strategies and the need for more comprehensive measures to restore the river’s self-purification capacity. It emphasizes the urgency of integrated and targeted approaches in combating pollution sources, enhancing reaeration, and promoting ecosystem-based solutions to revitalize the Citarum River and safeguard its ecological integrity for future generations.
4.3. Effect of Physicochemical Variables on Self-Purification
The reaeration rate in the upstream of the Citarum River is significantly influenced by physical parameters (i.e., PhysPC1 and PhysPC2) (
Table 1). The rate of reaeration may be enhanced by the physical and hydrological characteristic of the river [
50]. Physical water parameters (PhysPC1 and PhysPC2) such as water temperature, conductivity, transparency, TDS, and TSS strongly influence the reaeration process. The factors of temperature and transparency positively influence the reaeration rate in water bodies, and this means that temperature and transparency have synergistic effects on the reaeration rate. Meanwhile, the conductivity, TDS, and TSS factors have negative effects on the reaeration rate.
Temperature, TDS, TSS, conductivity, and transparency have different impacts on the reaeration rate. Aquatic ecosystems are sensitive to the influence of temperature [
51]. One of the primary mechanisms of this influence is the increase in the gas transfer coefficient at higher temperatures [
52]. The rate of atmospheric oxygen absorption at the air–water interface increases with increasing temperatures due to decreases in the viscosity, density, and surface tension [
53]. Elmore and West [
53] found that the reaeration rate increases geometrically with the increasing temperature. This leads to an increased transfer of oxygen from the atmosphere into the water, resulting in a higher reaeration rate. Additionally, higher temperatures can enhance the molecular diffusion of oxygen. As temperatures rise, the kinetic energy of oxygen molecules increases, resulting in accelerated rates of diffusion [
54]. This facilitates the transfer of oxygen across the air–water interface, further contributing to a higher reaeration rate.
Total dissolved solid (TDS) contaminants were found in the urban area at a concentration of 424.67 mg/L. Majalaya is an urban area with settlements and industry, so much of the waste produced is dissolved in the water. The TDS value has also been correlated with conductivity. TDS and conductivity can affect reaeration rates in water bodies through increased ionic strength and a decrease in the diffusion coefficients of gases [
55]. High TDS and conductivity levels result in higher concentrations of dissolved ions, making it harder for gases like oxygen to dissolve into the water [
55,
56]. This decreased solubility limits the reaeration process, reducing the overall reaeration rate. Additionally, certain dissolved substances associated with a high conductivity can undergo electrochemical reactions that consume dissolved oxygen, further impeding reaeration.
The land around the Cihawuk segment is a horticultural area with a high slope and no barrier between it and the river. Agricultural activities such as watering, fertilizer or pesticide application, along with rain, cause runoff from the land, which results in particles rapidly entering the water body and remaining in suspension in the water. Suspended particles (TSS) can cause water to become turbid and can decrease transparency, as was evident in the Cihawuk segment. The attenuation of light penetration limits the photosynthetic activity of aquatic plants [
57,
58] and can thus impact the reaeration rate; the decrease in photosynthesis leads to a lower oxygen production, which directly affects the reaeration rate [
59]. Moreover, suspended solids can settle and be deposited on the riverbed, forming layers that hinder gas exchange with the atmosphere. This deposition reduces the available surface area for reaeration, further decreasing the reaeration rate.
Based on our PCR calculation, deoxygenation in the upstream of the Citarum River waters is only influenced by chemical parameters (i.e., ChemPC2). The deoxygenation process is simultaneously influenced by physical, chemical, and biological parameters. However, this study is limited to measuring the physicochemical parameters only. Therefore, of the parameters considered in this study, only the ChemPC2 factor was found to influence self-purification during the PCR process. The ChemPC2 factor significantly affects the deoxygenation process through BOD and TOM, which were found to have significant negative impacts on the deoxygenation rate in the Citarum River. High BOD and TOM concentrations are related to the presence of increased concentrations of biodegradable organic matter, which leads to increased microbial activity and, consequently, increased oxygen consumption, resulting in a higher deoxygenation rate.
In the case of the upstream of the Citarum River, the BOD and TOM concentrations have an antagonistic effect on the deoxygenation rate. It is important to consider that the specific impact of BOD and TOM on the deoxygenation rate can vary depending on factors such as the composition and quality of the organic matter, microbial activity, oxygen availability, environmental conditions, and other factors and processes in the water body. The deoxygenation rate in the Cihawuk segment is low, despite physicochemical factors such as high oxygen concentrations. This is due to the composition and quality of organic materials in this segment of the river, which cannot be easily decomposed, and is also due to environmental conditions related to the non-point diffusion of agricultural pollutants that affect the deoxygenation rate. Meanwhile, the deoxygenation rate in the Majalaya segment is relatively low because oxygen availability is quite low in that segment. The low oxygen availability is due to a high organic matter content in the industrial and domestic pollutants entering the river, which inhibits the decomposition process.