Development of an accurate optical sensor for the in situ real-time determination of the chemical oxygen demand of seawater.

Chemical oxygen demand (COD) is an important indicator for monitoring the quality of seawater. The COD of seawater reflects the levels of organic pollutants in the water. Methods that are commonly used to measure the COD of seawater have high accuracy, good repeatability, and low costs. However, using them for the in situ real-time monitoring of the COD of seawater is unfavorable because they require complex procedures and a long measurement time and may cause pollution to the environment. This paper reports on an optical sensor that accurately determines the COD of seawater in situ. The COD determination is based on the absorption of ultraviolet and visible lights with different wavelengths by organic matter in the water. Single-point LEDs emitting lights with different wavelengths (254, 265, 280, and 546 nm) were used as sources of excitation lights, and photodiodes were used as receiving devices. The optical system, circuit system, and mechanical structure of the sensor were efficiently integrated. The inversion of the COD of seawater was obtained after turbidity correction using the multiple linear regression algorithm. The maximum measurement error, detection limit, and repeatability of the sensor were 5%, 0.05 mg/l, and 0.62%, respectively. Moreover, the R2 values for correlations between COD values and absorbance values measured at three wavelengths (254, 265, and 280 nm) were above 0.99. Overall, the sensor is suitable for the in situ real-time monitoring of the COD of seawater. It requires a short measurement time and generates no pollution.

Surface-Enhanced Raman Spectroscopy (SERS) Activity of Gold Nanoparticles Prepared Using an Automated Loop Flow Reactor.

This study used automatic control methods to prepare gold nanoparticles (AuNPs) as the substrate and rhodamine 6G molecule as the probe to investigate the enhancement effect, stability, and consistency of surface-enhanced Raman spectroscopy (SERS). The gold nanosols were prepared via automatic control using loop flow-reactor technology, and the synthesis of nanoparticles with different sizes was precisely controlled by optimizing the ratio of the solution required for the reaction between sodium citrate and chloroauric acid during the preparation process. The morphology, structure, and optical properties of the prepared AuNPs were investigated using field-emission scanning electron microscopy, transmission electron microscopy, and ultraviolet visible spectroscopy. Using the proposed method, AuNPs with average particle sizes of 72, 85, 93, and 103 nm were synthesized in a precisely controlled manner. The 93 nm particles exhibited good SERS activity for rhodamine 6G under 785 nm excitation with a detection limit of 2.5 × 10-10 M. The relative standard deviation of the SERS spectra synthesized multiple times was <3.5%, indicating their good sensitivity and reproducibility. The results showed that the AuNPs prepared by the automatic control of the loop-flow method have high sensitivity, stability, and reproducibility. Moreover, they exhibited notable potential for in situ measurement and quantitative analysis using SERS.

[Detection of High Molecular Weight Polycyclic Aromatic Hydrocarbons in Mixed Colloid Solution of Spherical Au and Urchin-Like Au-Ag Alloy with Surface-Enhanced Raman Scattering].

In this paper, Au nanosphere and Au-Ag alloy nanourchin were prepared by reducing the chloroauric acid. The mixed colloid solutions of Au nanosphere and Au-Ag alloy nanourchin were used as surface-enhanced Raman scattering (SERS) substrate to detect polycyclic aromatic hydrocarbons (PAHs) in aqueous solution. The size of Au-Ag alloy nanourchin particle was about 300~400 nm and the thorn-like bulge covered on it was about 40~100 nm. The mixed colloid solutions of Au nanosphere and Au-Ag alloy nanourchin which were optimized pH values and other parameters presented a better enhancement than Au nanosphere. The enhancement effect was about three times that of Au nanosphere colloid solution. Three kinds of high molecular weight PAHs, pyrene(4 rings), benzoanthracene(4 rings) and benzo[a]pyrene(5 rings), were detected. The results showed that there were good linear relationships between Raman intensity and concentration in the low concentration range and the mixed SERS substrate had a good reproducibility and stability. Their limits of detection (LODs) were 0.44, 2.92 and 1.64 nmol·L-1, respectively. The innovation of this paper was that the mixed colloid solutions of Au nanosphere and Au-Ag alloy nanourchin are prepared as SERS substrate and the trace-level high molecular weight PAHs are detected. The results show that the detection of trace-level high molecular weight PAHs in aqueous can be realized using the mixed SERS substrate prepared in this study, which proposed an in-situ method for detecting the high molecular weight PAHs in aqueous.