A Direct Bicarbonate Detection Method Based on a Near-Concentric Cavity-Enhanced Raman Spectroscopy System

Raman spectroscopy has great potential as a tool in a variety of hydrothermal science applications. However, its low sensitivity has limited its use in common sea areas. In this paper, we develop a near-concentric cavity-enhanced Raman spectroscopy system to directly detect bicarbonate in seawater for the first time. With the aid of this near-concentric cavity-enhanced Raman spectroscopy system, a significant enhancement in HCO3− detection has been achieved. The obtained limit of detection (LOD) is determined to be 0.37 mmol/L—much lower than the typical concentration of HCO3− in seawater. By introducing a specially developed data processing scheme, the weak HCO3− signal is extracted from the strong sulfate signal background, hence a quantitative analysis with R2 of 0.951 is made possible. Based on the spectra taken from deep sea seawater sampling, the concentration of HCO3− has been determined to be 1.91 mmol/L, with a relative error of 2.1% from the reported value (1.95 mmol/L) of seawater in the ocean. It is expected that the near-concentric cavity-enhanced Raman spectroscopy system could be developed and used for in-situ ocean observation in the near future

Natural Gas Hydrate CT Image Threshold Segmentation Based on Time Evolution

Micro-scale X-ray computed tomography (CT) has been widely used to study the occurrence forms of gas hydrate-bearing sediments. However, the similarity between the X-ray attenuation coefficient of hydrate and that of water leads to a strong non-uniqueness in their phase differentiation in CT images. To improve threshold segmentation accuracy between hydrate and water in CT images, this study proposes a CT image and histogram normalized method by analyzing the histogram characteristics of CT images at different times during the growth process of natural gas hydrate. First, the peak gray value baseline of methane gas and quartz sand was selected. Then, a Gaussian function was used to fit the curves corresponding to methane gas and quartz sand in the current CT image histogram to obtain the peak gray values. In addition, the peak gray values of methane gas and quartz sand in the current CT image histogram were normalized to the chosen peak gray baseline. Subsequently, the normalized histogram was used to normalize the corresponding CT images. Finally, according to the changing trend of normalized gray histogram curves, the increasing gray ranges of hydrate and decreasing gray ranges of gas-water in CT images were obtained quantitatively, which guided threshold segmentation of CT images. Experimental results show that the proposed threshold segmentation method can provide a basis for phase differentiation between hydrate and water in CT images, improving the threshold segmentation accuracy

Investigation of Two Novel Approaches for Detection of Sulfate Ion and Methane Dissolved in Sediment Pore Water Using Raman Spectroscopy

The levels of dissolved sulfate and methane are crucial indicators in the geochemical analysis of pore water. Compositional analysis of pore water samples obtained from sea trials was conducted using Raman spectroscopy. It was found that the concentration of SO42− in pore water samples decreases as the depth increases, while the expected Raman signal of methane has not been observed. A possible reason for this is that the methane escaped after sampling and the remaining concentration of methane is too low to be detected. To find more effective ways to analyze the composition of pore water, two novel approaches are proposed. One is based on Liquid Core Optical Fiber (LCOF) for detection of SO42−. The other one is an enrichment process for the detection of CH4. With the aid of LCOF, the Raman signal of SO42− is found to be enhanced over 10 times compared to that obtained by a conventional Raman setup. The enrichment process is also found to be effective in the investigation to the prepared sample of methane dissolved in water. By CCl4 extraction, methane at a concentration below 1.14 mmol/L has been detected by conventional Raman spectroscopy. All the obtained results suggest that the approach proposed in this paper has great potential to be developed as a sensor for SO42− and CH4 detection in pore water

Analysis and Modeling Methodologies for Heat Exchanges of Deep-Sea In Situ Spectroscopy Detection System Based on ROV

In recent years, cabled ocean observation technology has been increasingly used for deep sea in situ research. As sophisticated sensor or measurement system starts to be applied on a remotely operated vehicle (ROV), it presents the requirement to maintain a stable condition of measurement system cabin. In this paper, we introduce one kind of ROV-based Raman spectroscopy measurement system (DOCARS) and discuss the development characteristics of its cabin condition during profile measurement process. An available and straightforward modeling methodology is proposed to realize predictive control for this trend. This methodology is based on the Autoregressive Exogenous (ARX) model and is optimized through a series of sea-going test data. The fitting result demonstrates that during profile measurement processes this model can availably predict the development trends of DORCAS’s cabin condition during the profile measurement process

A New Approach of Oil Spill Detection Using Time-Resolved LIF Combined with Parallel Factors Analysis for Laser Remote Sensing

In hope of developing a method for oil spill detection in laser remote sensing, a series of refined and crude oil samples were investigated using time-resolved fluorescence in conjunction with parallel factors analysis (PARAFAC). The time resolved emission spectra of those investigated samples were taken by a laser remote sensing system on a laboratory basis with a detection distance of 5 m. Based on the intensity-normalized spectra, both refined and crude oil samples were well classified without overlapping, by the approach of PARAFAC with four parallel factors. Principle component analysis (PCA) has also been operated as a comparison. It turned out that PCA operated well in classification of broad oil type categories, but with severe overlapping among the crude oil samples from different oil wells. Apart from the high correct identification rate, PARAFAC has also real-time capabilities, which is an obvious advantage especially in field applications. The obtained results suggested that the approach of time-resolved fluorescence combined with PARAFAC would be potentially applicable in oil spill field detection and identification

Development of an Easy-to-Operate Underwater Raman System for Deep-Sea Cold Seep and Hydrothermal Vent In Situ Detection

As a powerful in situ detection technique, Raman spectroscopy is becoming a popular underwater investigation method, especially in deep-sea research. In this paper, an easy-to-operate underwater Raman system with a compact design and competitive sensitivity is introduced. All the components, including the optical module and the electronic module, were packaged in an L362 × Φ172 mm titanium capsule with a weight of 20 kg in the air (about 12 kg in water). By optimising the laser coupling mode and focusing lens parameters, a competitive sensitivity was achieved with the detection limit of SO42− being 0.7 mmol/L. The first sea trial was carried out with the aid of a 3000 m grade remotely operated vehicle (ROV) “FCV3000” in October 2018. Over 20,000 spectra were captured from the targets interested, including methane hydrate, clamshell in the area of cold seep, and bacterial mats around a hydrothermal vent, with a maximum depth of 1038 m. A Raman peak at 2592 cm−1 was found in the methane hydrate spectra, which revealed the presence of hydrogen sulfide in the seeping gas. In addition, we also found sulfur in the bacterial mats, confirming the involvement of micro-organisms in the sulfur cycle in the hydrothermal field. It is expected that the system can be developed as a universal deep-sea survey and detection equipment in the near future

Elemental analysis of powders with surface-assisted thin film laser-induced breakdown spectroscopy

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