3.2. Technologies for Chemical Monitoring of Water Quality
3.2.1. Chlorine
Chlorine is one of the main disinfectants in public water supplies since its oxidizing characteristic can eliminate pathogenic microorganisms present in the water
[71]. Therefore, detecting the concentration of free chlorine in the water is essential for monitoring and detecting the presence of contaminants. The consolidation of free chlorine sensors in water has taken place gradually, so that, even after many years have passed since the first attempts, many sensors are still under development and improvement. The development of new technologies for chlorine measurement will be described below, as well as presented in
Table 4.
Table 4. Summary of studies that present new alternative technologies for monitoring the chlorine parameter in water.
Author(s) |
Type |
Description |
Research Findings |
Cassidy et al. [72] |
Optical |
Developed a spectrophotometric device for chlorine detection in real-time using a xenon light source and a flow sample chamber. |
Device performed well, but improvements are needed for field application. |
Hall et al. [73] |
Optical and Electrical |
Assessed electrical and optical sensors for chlorine detection in water. |
The sensors were able to determine chlorine with good accuracy, but more analysis is needed to improve the devices. |
Gimenez-Gomez et al. [74] |
Electrical |
Presented a low-cost, compact portable multisensory electronic system to measure parameters of water quality. |
The device presented good performance compared to commercial equipment, including free chlorine analysis. |
Cui et al. [75] |
Described the development of a microcontroller system, with wireless communication, to measure water quality parameters. |
The device allowed online communication and the commercial residual chlorine sensor used (free chlorine and monochloramine) showed good results. |
Yen et al. [76] |
Developed a low-cost chemo-resistive sensor based on nanohybrid paper to measure free chlorine ions. |
The developed sensor showed a linear range of 0.1−500 ppm, and the limit of detection was 0.18 ppm. |
Alam et al. [77] |
Proposed a reusable, reagent-free sensor based on a thin gold film for chlorine measurement. |
The sensor showed high-sensitivity accuracy, like commercial sensors. |
Cassidy et al.
[72], for example, studied a low-cost spectrophotometric sensor for chlorine detection with real-time data collection capability, aimed at increasing the acquisition time and improving the mechanical stability of chlorine sensors. The main components of this optical system were a xenon light source and a flow sample chamber. For communication, a DSP (Digital Signal Processor, EVM56303, produced by Motorola, Austin, TX, USA) board was used, which provides control signals and interacts with external devices. Overall, the device performed positively in the laboratory, but improvements are still pending for field applications and real-world scenarios.
Hall et al.
[73] focused on the detection of parameters online to indicate contamination in the distribution system, using commercial sensors, including free chlorine sensors. Altogether, three sensors with different chlorine detection principles (colorimetric, polarographic, and voltammetric) were tested with costs ranging from US$3000 to US$10,000. The free chlorine was the best parameter, among the analyzed parameters, which responded to the presence of contaminants, but the authors point out that the technologies used were still in the consolidation phase and needed future improvements.
The quest to improve and reduce the costs of chlorine measurement was also presented by Gimenez-Gomez et al.
[74], who proposed a compact portable device to simultaneously measure five water quality parameters, including amperometric parameters, using microelectronic technology with low power consumption. The electronic system was tested, and the analytical signals were compared with commercial equipment. In addition, the authors claim that the communication between the computer and the portable device can be carried out using a wireless protocol, such as a Wi-Fi or a low-power ZigBee interface.
To facilitate and modernize the detection of contaminants, Cui et al.
[75] designed a Water Quality Monitoring System based on the
STM32F103 microcontroller integrated system and the
nRF24L01 wireless communication module. Various types of sensors were used to detect harmful components in the water, including the commercial residual chlorine sensor
CLE3-DMT to detect free chlorine and monochloramine. The system’s proposal was to allow users to use their smartphones to carry out the real-time and online monitoring of various parameters in water quality. As the system has been successful in experiments, the authors believe that the device can be widely used with further research.
With the objective of facilitating portability, Yen et al.
[76] also broke new ground in chlorine monitoring and presented a chemo-resistive sensor based on a nanohybrid paper that can be used with smartphones to detect free chlorine ions. The sensor was manufactured using a simple, standardized coating process on graphene paper and PEDOT:PSS, whose results presented a linear range of 0.1–500 ppm for free chlorine measurement, with a detection limit of 0.18 ppm. The sensor was integrated into an electrical reading system, using
Arduino Uno Rev3 SM (Arduino, Genoa, Italy), designed for miniaturization and wireless transmission to a smartphone by a Bluetooth module. The authors emphasize that the system is advantageous for its portability, low cost, and allowing real-time readings on a smartphone.
Furthermore, the innovation of chlorine sensors is ongoing, as shown by Alam et al.
[77], who developed a reusable, reagent-free sensor based on a thin gold film. The sensor presented high sensitivity, which is often a challenge for other commercial sensors, and due to simple fabrication and good detection performance, the proposed device enables mass production and future application in distant regions with low investment.
3.2.2. Dissolved Oxygen (OD)
Dissolved oxygen (DO) is an important parameter in water quality and essential for aquatic life. According to Hou et al.
[78], when the DO concentration is less than 3 mg/L, there is an impact on the health of the fish, which can even lead to death by asphyxia. Furthermore, according to Hsu et al.
[79], a low concentration of DO can negatively affect a water system by facilitating the excessive growth of anaerobic bacteria. The DO concentration can also indicate various contaminants in water bodies, making DO one of the most important parameters for monitoring.
There are two types of DO sensors: electrochemical and optical. Electrochemical DO sensors are based on the electrical current produced to measure the concentration of dissolved oxygen in water and can be polarographic or galvanic
[80]. Optical DO sensors, also called luminescent DO sensors (LDO), measure the concentration of dissolved oxygen in water according to the extinction of luminescence in the presence of oxygen, being able to measure the intensity or lifetime of luminescence, since oxygen affects both
[81].
Research to optimize DO measurement technologies is directed towards both electrochemical and optical sensors, however, DO electrochemical sensors are currently seen as more promising and are more widely used, mainly because they perform online in situ measurements
[80]. The following works present the advances in technologies for DO measurement in water, as summarized in
Table 5 also. Thus, in situ and online monitoring systems for aquaculture and other water uses have been using commercial dissolved oxygen sensors with electrochemical detection, as described by Liu
[82], Luo et al.
[83], Vijayakumar and Ramya
[84], and He
[85]. Liu
[82] and He
[85] were able to monitor OD and other water quality parameters (turbidity, pH, temperature, and electrical conductivity) for fishery management based on the IoT concept. From the same approach, Vijayakumar and Ramya
[84] also were able to measure DO in water for aquaculture management using a Raspberry PI B+ core controller and an IoT module (USR WIFI 232). Finally, Luo et al.
[83] used a commercial YCS-2000 dissolved oxygen sensor and Zigbee and GPRS modules to monitor water quality parameters in real-time at a low cost, including DO.
Table 5. Summary of studies that present new alternative technologies for monitoring the dissolved oxygen parameter in water.
Author(s) |
Type |
Description |
Research Findings |
Liu [82] |
Electrical |
Designed an IoT system for monitoring the water quality environment for fishing in real-time. |
The system was able to acquire DO, turbidity, pH, temperature, and electrical conductivity parameters in real-time, storing them in a database. |
Luo et al. [83] |
Developed a real-time monitoring system to measure DO in water using a YCS-2000 sensor. |
The system could fulfill the real-time remote monitoring of aquaculture water quality and had great practical significance in the reduction in labor intensity. |
Vijayakumar and Ramya [84] |
Present a low-cost system for real-time water quality monitoring (including DO) using a Raspberry PI B+ model. |
The device was presented as a low-cost and real-time monitoring system, being capable of processing, analyzing, sending, and viewing the data in the cloud. |
He [85] |
Designed and developed an embedded aquaculture intelligent water quality monitoring system based on STM32F103VET6. |
The system could provide technical support for the design and development of an aquaculture monitoring system. |
Lee et al. [86] |
Designed a DO sensor for in situ water quality analysis using a needle-like microelectrode arrangement (MEA). |
The DO MEA exhibited a rapid 15 s linear response in the 0–9 mg/L (0–21% O | 2 | ) range. |
Penso et al. [87] |
Optical |
Used a PDMS membrane coated with a platinum octaethylporphyrin (PtOEP) film to measure DO in water. |
In a liquid medium, the sensor was able to measure DO in a range of 0–5.5 mg/L. |
Mahoney et al. [88] |
Optimized a multilayer optical-fluidic sensor for DO in situ measurement. |
The results showed a comparable sensitivity and sensing range (0–20 ppm) compared to previously developed miniaturized DO sensors. |
The development of new technologies for DO sensors is ongoing, as presented, for example, by Lee et al.
[86], who studied a new DO sensor for in situ water analysis with a needle-like microelectrode arrangement, obtained by microfabrication technologies, which aims to integrate sensors with IC (Integrated Circuit) chips for online data acquisition. Thus, the authors obtain a rapid 15 s linear response in the 0–9 mg/L (0–21% O
2) range. Penso et al.
[87] described the development, fabrication, and characterization of a low-cost, high-sensitivity optical sensor for DO detection with the potential for in situ measurement in a marine environment (between 0 and 5.5 mg/L) based on a PDMS membrane coated with a platinum octaethylporphyrin (PtOEP) film. Mahoney et al.
[88] also innovated the optimization of a multilayer optical-fluidic sensor device based on the measurement of fluorescence suppression in a ruthenium-based oxygen-sensitive dye to obtain increased sensitivity in the in situ detection of DO in water between 0 and 20 ppm.