A comparison between high temperature catalytic and persulfate oxidation for the determination of total dissolved nitrogen in natural waters
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Abstract: Total dissolved nitrogen (TDN) is an important parameter for assessing the nutrient cycling and status of natural waters. The accurate determination of TDN in natural waters is essential for assessing its contents and distinguishing different forms of nitrogen in the water. The TDN in various systems has been largely documented, and the concentrations of TDN are usually obtained using high-temperature catalytic (HTC) or persulfate oxidation (PO). However, the accuracy of these methods and their suitability for all types of natural waters are still unclear. To explore both methods in-depth, assorted samples were tested, including eight solutions composed of nitrogen-containing compounds (3 dissolved inorganic nitrogen fractions:
${{\rm {NO}}_3^-}$ ,${{\rm {NO}}_2^-} $ and${{\rm {NH}}_4^+} $ ; 5 organic compounds: EDTA-2Na, vitamin B1, vitamin B12, amino acids, and urea) and 105 natural waters which were collected from an open ocean (Northwest Pacific Ocean, 28), a marginal sea (Yellow Sea, 34), an estuary (Huanghe River mouth, 31), rivers (Huanghe River, 4; Licun River, 4), and precipitations (4 samples). The results showed that heterocycles and molecular dimensions had certain effects on the oxidation efficiency of the PO method but had little effect on HTC. There was no significant difference between the two methods for natural waters, but HTC was more suitable for deep-sea samples with low TDN concentrations (less than 10 μmol/L) and low organic activity. Overall, HTC has a relatively simple measurement process, a high degree of automation, and low error. Therefore, HTC can be recommended to determine the TDN of samples in freshwater and seawater. -
Figure 1. Locations of natural waters sampling. The triangle is the location of the Ocean University of China.
Figure 2. Scatter plot of the results of the tested compound solution by high-temperature catalytic (HTC) and persulfate oxidation (PO). Dotted lines are the regression lines of vitamin B1 (VB1), VB12, and EDTA-2Na. Black line is the 1:1 line of best fit. AAS: amino acids.
Figure 3. Relative difference between persulfate oxidation (PO) and high-temperature catalytic (HTC) data as a function of total dissolved nitrogen (TDN) concentration for the tested compound solutions.
Figure 4. Scatter plot of the results of the natural waters by high-temperature catalytic (HTC) and persulfate oxidation (PO). Dotted lines are regression lines of all of the natural samples. Black line is the 1:1 line of best fit.
Figure 5. Relative difference between persulfate oxidation (PO) and high-temperature catalytic (HTC) data as a function of total dissolved nitrogen (TDN) concentration for natural water samples.
Figure 6. Recovery between measured nitrogen data and nominal N concentration for different solutions, VB1 (a), VB12 (b), EDTA-2Na (c) and the other tested compounds (d). The solid dots represent high-temperature catalytic (HTC), and the hollow dots represent persulfate oxidation (PO).
Figure 7. Scatter plots of results of the open ocean, the marginal sea, an estuary, and freshwater by high-temperature catalytic (HTC) and persulfate oxidation (PO). Dotted lines are regression lines. Black lines are the 1:1 line of best fit.
Figure 8. Depth profile of total dissolved nitrogen (TDN) measurements by the high-temperature catalytic (HTC) and persulfate oxidation (PO) methods in the Northwest Pacific. Error bars represent the standard deviation for each sample after three analyses.
Table 1. Natural water samples and their collection information
Sample type Site Location Sampling date Number Open ocean Northwest Pacific Ocean 13°−40°N, 150°E November 2019 28 Marginal sea Yellow Sea 35.94°−36.13°N, 120.27°−126.27°E March 2019 34 Estuary Huanghe River mouth 37.83°−38.32°N, 118.08°−119.26°E October 2019 31 River water Huanghe River 37.61°N, 118.54°E November 2019 4 Licun River 36.16°N, 120.47°E November 2019 4 Precipitations Qingdao, China 36.16°N, 120.50°E July 2019 and January 2020 4 
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