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The evaluation for alterations of DOM components from upstream to downstream flow of rivers in Toyama (Japan) using three-dimensional excitation-emission matrix fluorescence spectroscopy.

Sazawa K, Tachi M, Wakimoto T, Kawakami T, Hata N, Taguchi S, Kuramitz H - Int J Environ Res Public Health (2011)

Bottom Line: However, the correlations between the RFI values for other four peaks and the DOC concentration were below 0.287.It was clarified that the great increase of RFI values in peak A and peak T from river water located in urban area showed high concentration of PO(4)-P and Fe(3+), and low N/P ratio due to the high biological activities.The values of fluorescence index (FIX) and biological index (BIX) were as high as 1.60 and 0.72, respectively.

View Article: PubMed Central - PubMed

Affiliation: Department of Environmental Biology and Chemistry, Graduate School of Science and Engineering for Research, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan. d1071303@ems.u-toyama.ac.jp

ABSTRACT
The dissolved organic matter (DOM) is one of the important factors for controlling water quality. The behavior and constitutions of DOM is related to the risk of human health because it is able to directly or indirectly affect the behavior, speciation and toxicity of various environmental pollutants. However, it is not easy to know the contents of DOM components without using various complicated and time consuming analytical methods because DOM is a complex mixture and usually exists at low concentration. Here, we describe the fluorescence properties of DOM components in water samples collected from four rivers in Toyama, Japan by means of the three-dimensional excitation-emission matrix (3DEEM) fluorescence spectroscopy. In order to evaluate the alterations of DOM components in each of the river during the flow from upstream to downstream, the patterns of relative fluorescence intensity (RFI) at six peaks which are originated from fluorophores including humic-like and protein-like components were investigated. The changes in the patterns of RFI values at each of the peak and the concentration of dissolved organic carbon (DOC) for each river water sample were discussed in connection with the differences of land use managements and basic water quality parameters, such as pH, EC, turbidity, Fe(3+), T-N, NO(3)-N, T-P, PO(4)-P, chlorophyll a, DOC and N/P ratio. The DOC concentrations in the water samples collected from these rivers were relatively low (0.63-1.16 mg/L). Two main peaks which have a strong RFI value expressed a positive correlation with the DOC concentration (r = 0.557, 0.535). However, the correlations between the RFI values for other four peaks and the DOC concentration were below 0.287. The alterations of DOM components during the flow of a river from upstream to downstream were investigated from the changes in the patterns of RFI values for six fluorescent peaks. It was clarified that the great increase of RFI values in peak A and peak T from river water located in urban area showed high concentration of PO(4)-P and Fe(3+), and low N/P ratio due to the high biological activities. The values of fluorescence index (FIX) and biological index (BIX) were as high as 1.60 and 0.72, respectively.

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The patterns of RFI values at six fluorescent peaks (peak C, peak A, peak M, peak N, peak B and peak T) obtained from 3DEEM spectra for each water sample collected from (a) Oyabe River; (b) Shou River; (c) Jinzu River; and (d) Jyouganji River.
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f4-ijerph-08-01655: The patterns of RFI values at six fluorescent peaks (peak C, peak A, peak M, peak N, peak B and peak T) obtained from 3DEEM spectra for each water sample collected from (a) Oyabe River; (b) Shou River; (c) Jinzu River; and (d) Jyouganji River.

Mentions: The evaluation for the alteration of DOM components during the flow was demonstrated by the patterns of RFI at six fluorescence peaks obtained from the 3DEEM spectra for each river water sample, as shown in Figure 4. The RFI values for peak C, peak A, peak M, peak N, peak B and peak T were read from the position at 320/420, 240/420, 290/370, 280/370, 270/370 and 220/345 (Ex./Em.) nm, respectively. The results from water samples of Oyabe River show that the RFI values of peak C gradually increased from upstream to downstream, and the value of peak A rapidly increased at site 4 [Figure 4(a)]. Moreover, the high RFI value at peak T which is related with tryptophan-like fluorophores had also risen at site 4. Although the DOC concentrations at site 1 and site 4 were similar, the patterns of RFI obtained from the six fluorescent peaks were drastically different. Namely, the qualitative changes of DOM components occurred between site 3 and site 4 where the urban area including industrial and sewage plant are located. As described above, there are two tributaries between site 1 and site 2 and three tributaries between site 3 and site 4 in Oyabe River. Although the concentration of NO3-N and PO4-P increased at both of site 2 and site 4, the qualitative changes of DOM components obtained from the patterns of RFI values were found at only urban area between site 3 and site 4 in Oyabe River. The RFI values of each of the peak obtained from 3DEEM spectrum for the finished water from the sewage plant are shown in Table 3. The main peak was peak C. The RFI values at all other peaks against the peak C were low compared with the patterns of RFI values at site 4 in Oyabe River [Figure 4 (a)]. Considering the low RFI values at peak T for the finished water, it can be assumed that the high RFI value at peak T of Oyabe River’s site 4 is most likely not directly related to the discharge from the sewage plant. It is unclear at this stage what causes the difference at the peak T’s RFI value (Oyabe River’s site 4). However, based on the information obtained from the land use management map and the fact that peak T is not observed on the mixture area of crops and paddies between site 1 and site 3 in Oyabe River, we could consider that to some extent, it is somehow related to industrial discharges. Taking into consideration the low value of N/P ratio and high concentration of PO4-P and Fe3+ at site 4 of Oyabe River, we could presume that the decomposition of DOM by biological actions in the river water might be linked to the generation of DOM components that resulted in the rise of peak T and peak A. In contrast to Oyabe River, changes in the patterns of RFI value at six fluorescent peaks from upstream to downstream were not observed in the results obtained from Shou River [Figure 4(b)]. Thus, it is expected that the quality of the DOM components in Shou River’s upstream is not so much different to the downstream. As shown in Table 1, the other water quality parameters of Shou River such as EC, T-N, NO3-N, Chl. a and DOC hardly changed. The change of DOM components in Jinzu River was observed between site 1 and site 2. The peak A which was not detected at site 1 appeared at site 2 [Figure 4(c)]. A similar phenomenon about peak A was also found at site 1 of Jyouganji River [Figure 4(d)]. This could be an influence from the paddy field which is located around these areas as according to the land use management map. As for the sample of paddy agricultural water, the respective RFI values for peak A, peak M and peak N were detected and are shown in Table 3. However, it is obvious that the RFI value was not high as expected for peak A. Therefore, the reason for the arisen of peak A cannot be clarified through this investigation. At site 4 in Jinzu River, an increment of DOC concentration was observed and this could a consequence of the industrial waste in the urban area. On the other hand, as in site 4 of Oyabe River, no qualitative changes of DOM components were observed from the patterns of RFI values. The difference observed at both site 4 of these two rivers is that the value of N/P ratio that acts as an indicator of biological activities was not low in Jinzu River, unlike in Oyabe River. This indicates that the generation of peak T and peak A observed in 3DEEM spectrum is suitable to detect the alteration of DOM components in water that has industrial discharge and low N/P ratio, i.e., high biological activities.


The evaluation for alterations of DOM components from upstream to downstream flow of rivers in Toyama (Japan) using three-dimensional excitation-emission matrix fluorescence spectroscopy.

Sazawa K, Tachi M, Wakimoto T, Kawakami T, Hata N, Taguchi S, Kuramitz H - Int J Environ Res Public Health (2011)

The patterns of RFI values at six fluorescent peaks (peak C, peak A, peak M, peak N, peak B and peak T) obtained from 3DEEM spectra for each water sample collected from (a) Oyabe River; (b) Shou River; (c) Jinzu River; and (d) Jyouganji River.
© Copyright Policy - open-access
Related In: Results  -  Collection

License 1 - License 2
Show All Figures
getmorefigures.php?uid=PMC3108133&req=5

f4-ijerph-08-01655: The patterns of RFI values at six fluorescent peaks (peak C, peak A, peak M, peak N, peak B and peak T) obtained from 3DEEM spectra for each water sample collected from (a) Oyabe River; (b) Shou River; (c) Jinzu River; and (d) Jyouganji River.
Mentions: The evaluation for the alteration of DOM components during the flow was demonstrated by the patterns of RFI at six fluorescence peaks obtained from the 3DEEM spectra for each river water sample, as shown in Figure 4. The RFI values for peak C, peak A, peak M, peak N, peak B and peak T were read from the position at 320/420, 240/420, 290/370, 280/370, 270/370 and 220/345 (Ex./Em.) nm, respectively. The results from water samples of Oyabe River show that the RFI values of peak C gradually increased from upstream to downstream, and the value of peak A rapidly increased at site 4 [Figure 4(a)]. Moreover, the high RFI value at peak T which is related with tryptophan-like fluorophores had also risen at site 4. Although the DOC concentrations at site 1 and site 4 were similar, the patterns of RFI obtained from the six fluorescent peaks were drastically different. Namely, the qualitative changes of DOM components occurred between site 3 and site 4 where the urban area including industrial and sewage plant are located. As described above, there are two tributaries between site 1 and site 2 and three tributaries between site 3 and site 4 in Oyabe River. Although the concentration of NO3-N and PO4-P increased at both of site 2 and site 4, the qualitative changes of DOM components obtained from the patterns of RFI values were found at only urban area between site 3 and site 4 in Oyabe River. The RFI values of each of the peak obtained from 3DEEM spectrum for the finished water from the sewage plant are shown in Table 3. The main peak was peak C. The RFI values at all other peaks against the peak C were low compared with the patterns of RFI values at site 4 in Oyabe River [Figure 4 (a)]. Considering the low RFI values at peak T for the finished water, it can be assumed that the high RFI value at peak T of Oyabe River’s site 4 is most likely not directly related to the discharge from the sewage plant. It is unclear at this stage what causes the difference at the peak T’s RFI value (Oyabe River’s site 4). However, based on the information obtained from the land use management map and the fact that peak T is not observed on the mixture area of crops and paddies between site 1 and site 3 in Oyabe River, we could consider that to some extent, it is somehow related to industrial discharges. Taking into consideration the low value of N/P ratio and high concentration of PO4-P and Fe3+ at site 4 of Oyabe River, we could presume that the decomposition of DOM by biological actions in the river water might be linked to the generation of DOM components that resulted in the rise of peak T and peak A. In contrast to Oyabe River, changes in the patterns of RFI value at six fluorescent peaks from upstream to downstream were not observed in the results obtained from Shou River [Figure 4(b)]. Thus, it is expected that the quality of the DOM components in Shou River’s upstream is not so much different to the downstream. As shown in Table 1, the other water quality parameters of Shou River such as EC, T-N, NO3-N, Chl. a and DOC hardly changed. The change of DOM components in Jinzu River was observed between site 1 and site 2. The peak A which was not detected at site 1 appeared at site 2 [Figure 4(c)]. A similar phenomenon about peak A was also found at site 1 of Jyouganji River [Figure 4(d)]. This could be an influence from the paddy field which is located around these areas as according to the land use management map. As for the sample of paddy agricultural water, the respective RFI values for peak A, peak M and peak N were detected and are shown in Table 3. However, it is obvious that the RFI value was not high as expected for peak A. Therefore, the reason for the arisen of peak A cannot be clarified through this investigation. At site 4 in Jinzu River, an increment of DOC concentration was observed and this could a consequence of the industrial waste in the urban area. On the other hand, as in site 4 of Oyabe River, no qualitative changes of DOM components were observed from the patterns of RFI values. The difference observed at both site 4 of these two rivers is that the value of N/P ratio that acts as an indicator of biological activities was not low in Jinzu River, unlike in Oyabe River. This indicates that the generation of peak T and peak A observed in 3DEEM spectrum is suitable to detect the alteration of DOM components in water that has industrial discharge and low N/P ratio, i.e., high biological activities.

Bottom Line: However, the correlations between the RFI values for other four peaks and the DOC concentration were below 0.287.It was clarified that the great increase of RFI values in peak A and peak T from river water located in urban area showed high concentration of PO(4)-P and Fe(3+), and low N/P ratio due to the high biological activities.The values of fluorescence index (FIX) and biological index (BIX) were as high as 1.60 and 0.72, respectively.

View Article: PubMed Central - PubMed

Affiliation: Department of Environmental Biology and Chemistry, Graduate School of Science and Engineering for Research, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan. d1071303@ems.u-toyama.ac.jp

ABSTRACT
The dissolved organic matter (DOM) is one of the important factors for controlling water quality. The behavior and constitutions of DOM is related to the risk of human health because it is able to directly or indirectly affect the behavior, speciation and toxicity of various environmental pollutants. However, it is not easy to know the contents of DOM components without using various complicated and time consuming analytical methods because DOM is a complex mixture and usually exists at low concentration. Here, we describe the fluorescence properties of DOM components in water samples collected from four rivers in Toyama, Japan by means of the three-dimensional excitation-emission matrix (3DEEM) fluorescence spectroscopy. In order to evaluate the alterations of DOM components in each of the river during the flow from upstream to downstream, the patterns of relative fluorescence intensity (RFI) at six peaks which are originated from fluorophores including humic-like and protein-like components were investigated. The changes in the patterns of RFI values at each of the peak and the concentration of dissolved organic carbon (DOC) for each river water sample were discussed in connection with the differences of land use managements and basic water quality parameters, such as pH, EC, turbidity, Fe(3+), T-N, NO(3)-N, T-P, PO(4)-P, chlorophyll a, DOC and N/P ratio. The DOC concentrations in the water samples collected from these rivers were relatively low (0.63-1.16 mg/L). Two main peaks which have a strong RFI value expressed a positive correlation with the DOC concentration (r = 0.557, 0.535). However, the correlations between the RFI values for other four peaks and the DOC concentration were below 0.287. The alterations of DOM components during the flow of a river from upstream to downstream were investigated from the changes in the patterns of RFI values for six fluorescent peaks. It was clarified that the great increase of RFI values in peak A and peak T from river water located in urban area showed high concentration of PO(4)-P and Fe(3+), and low N/P ratio due to the high biological activities. The values of fluorescence index (FIX) and biological index (BIX) were as high as 1.60 and 0.72, respectively.

Show MeSH
Related in: MedlinePlus