Copper is an essential element in living organisms and is crucial in marine ecosystems. However, excessive concentrations can lead to seawater pollution and pose a risk of toxicity to marine organisms, as it is a heavy metal. In addition, it can enter the human body through the food chain, potentially endangering human health. Consequently, there is increasing focus on the rapid and highly sensitive detection of copper ions (Cu2+). We prepared a graphite carbon electrode modified with graphitised multi-walled carbon nanotubes/copper(II) ion carrier IV (GMWCNT/copper(II) ion carrier IV/glassy carbon electrode (GCE)) using a drop-coating method. Scanning electron microscopy (SEM) analysis revealed that the composite material film possessed a large surface area. Incorporating this composite material significantly enhanced the adsorption capacity for ions on the electrode surface and greatly improved conductivity. Differential pulse anodic stripping voltammetry (DPASV) was employed to quantify copper levels in seawater. Under optimal experimental conditions, a strong linear relationship was observed between the Cu2+ response peak current and its concentration within a range of 50–500 µg L−1, with a correlation coefficient of 0.996. The GMWCNT/copper(II) ion carrier IV/GCE exhibited excellent stability and reproducibility, achieving a low detection limit for Cu2+ at 0.74 µg L−1 when applied to copper detection in seawater. Furthermore, spiked recovery rates ranging from 98.6% to 102.8% demonstrated the method’s high sensitivity, convenient operation, and practical value for real-world applications in detecting Cu2+ levels in seawater.
Phenanthrene (PHE), as a structurally simple, tricyclic, polycyclic aromatic hydrocarbon (PAHs), is widely present in marine environments and organisms, with serious ecological and health impacts. It is crucial to study fast and simple high-sensitivity detection methods for phenanthrene in seawater for the environment and the human body. In this paper, a immunosensor was prepared by using a multi-wall carbon nanotube (MWCNTs)-chitosan oligosaccharide (COS) nanocomposite membrane loaded with phenanthrene antibody. The principle was based on the antibody–antigen reaction in the immune reaction, using the strong electron transfer ability of multi-walled carbon nanotubes, coupled with chitosan oligosaccharides with an excellent film formation and biocompatibility, to amplify the detection signal. The content of the phenanthrene in seawater was studied via differential pulse voltammetry (DPV) using a potassium ferricyanide system as a redox probe. The antibody concentration, pH value, and probe concentration were optimized. Under the optimal experimental conditions, the response peak current of the phenanthrene was inversely proportional to the concentration of phenanthrene, in the range from 0.5 ng·mL−1 to 80 ng·mL−1, and the detection limit was 0.30 ng·mL−1. The immune sensor was successfully applied to the detection of phenanthrene in marine water, with a recovery rate of 96.1~101.5%, and provided a stable, sensitive, and accurate method for the real-time monitoring of marine environments.
Hg(II), as an extremely hazardous heavy metal contaminant in the environment, poses a significant potential hazard to human health and ecosystems. A GR-MWCNTs-COOH/CeO2/Nafion composite film-modified glassy carbon electrode was prepared using the drop-casting method in this study. The GR-MWCNTs-COOH/CeO2/Nafion/GCE was electrochemically investigated through cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV). Additionally, the surface morphologies of the composite film were evaluated using scanning electron microscopy (SEM). The conditions, such as buffer solution, pH, deposition potential, deposition time, modified film thickness, and Nafion content, were optimized. Under optimal experimental conditions, a good linear relationship between the peak current response of Hg(II) and its concentration in the range of 5–100 μg·L−1 was observed, with a detection limit of 0.389 μg·L−1. When it was used to detect Hg(II) in offshore seawater, the recovery rate ranged from 94.72% to 103.8%, with RSDs ≤ 5.79%.
Considering that heavy-metal contamination of seawater is getting worse, building a quick, accurate and portable device for detecting trace zinc in seawater in real time would be very beneficial. In this work, a microfluidic system was developed that includes a planar disc electrode, a micro-cavity for detection, an electrochemical workstation, a computer, a container for waste liquid reprocessing, an external pipeline and other components as well as a graphene/cerium oxide/nano-cerium oxide/Nafion composite membrane was used to modify the planar disc electrode (GR/CeO2/Nafion/Au) to investigate the electrochemical behaviour of Zn(II) using cyclic voltammetry, square-wave voltammetry and orthogonal test methods. Under optimal experimental conditions, the peak reaction current of Zn(II) showed a good linear relationship with the concentration of Zn(II) in the range of 1–900 μg/L with a correlation coefficient of 0.998, and the detection limit of the method was 0.87 μg/L. In addition, the microfluidic system had good stability, reproducibility and anti-interference. The system was used for determining zinc ions in real seawater samples, and the results were very similar to those of inductively coupled plasma–emission spectrometry, demonstrating the practicality of the system for the detection of trace zinc.
Cadmium (Cd) and zinc (Zn) in seawater enter the human body through the food chain. Combined toxicity tests indicated that high concentrations of Cd(II) and low concentrations of Zn(II) had a synergistic effect on humans. Thus, there is an urgent need to prepare a sensor for rapid and simultaneous detection of Cd(II) and Zn(II) in seawater. Herein, a reduced graphene oxide/carboxylated multi-walled carbon nanotube (rGO/MWCNT-COOH)-modified glassy carbon electrode was prepared in the experiments using the dropping method. The synthesis of various materials achieved the purpose of expanding the surface area, and scanning electron microscopy was used to observe the structure of the composite membrane. Moreover, the large number of functional groups on the surface of the composite membrane can also increase the adsorption of ions. For the determination of trace cadmium (II) and zinc (II) in seawater, the method used was differential pulse voltammetry (DPV). The results show that the peak current, which was obtained in the range of 5–400 μg/L for Cd(II) and Zn(II), has a linear relationship with concentration, corresponding to the detection limits of 0.8 μg/L for Cd(II) and 0.98 μg/L for Zn(II). The modified electrode was used to determine the Cd(II) and Zn(II) content in the coastal seawater of the Maowei Sea, and the recovery rate was between 95.8 and 98.2% for Cd(II) and 96.7~99.4% for Zn(II), which provided a novel approach of detection to define trace Cd(II) and Zn(II) in seawater.
7,12-Dimethylbenzo[a]anthracene (DMBA-7,12), a highly toxic and environmentally persistent polycyclic aromatic hydrocarbon (PAH), poses significant threats to marine biodiversity and human health due to its bioaccumulation through the food chain. Conventional chromatographic methods, while achieving comparable detection limits, are hindered by the need for expensive instrumentation and prolonged analysis times, rendering them unsuitable for rapid on-site monitoring of DMBA-7,12 in marine environments. Therefore, the development of novel, efficient detection techniques is imperative. In this study, we have successfully developed an electrochemical immunosensor based on a polydopamine (PDA)–chitosan (CTs) composite interface to overcome existing technical limitations. PDA provides a robust scaffold for antibody immobilization due to its strong adhesive properties, while CTs enhances signal amplification and biocompatibility. The synergistic integration of these materials combines the high efficiency of electrochemical detection with the specificity of antigen–antibody recognition, enabling precise qualitative and quantitative analysis of the target analyte through monitoring changes in the electrochemical properties at the electrode surface. By systematically optimizing key experimental parameters, including buffer pH, probe concentration, and antibody loading, we have constructed the first electrochemical immunosensor for detecting DMBA-7,12 in seawater. The sensor achieved a detection limit as low as 0.42 ng/mL. In spiked seawater samples, the recovery rates ranged from 95.53% to 99.44%, with relative standard deviations (RSDs) ≤ 4.6%, demonstrating excellent accuracy and reliability. This innovative approach offers a cost-effective and efficient solution for the in situ rapid monitoring of trace carcinogens in marine environments, potentially advancing the field of marine pollutant detection technologies.