Genki Matsumoto

Gas chromatographic-mass spectrometric identification of phenols and aromatic acids in river waters

Abstract The ethyl acetate extracts of water samples from two urban rivers in Tokyo were analyzed for phenols and aromatic acids by using a combined gas chromatograph-mass spectrometer after separating by solvent extraction and silica gel column chromatography. The following phenols and aromatic acids were identified: pentachlorophenol, bisphenol A, phthalic acid, trimesic acid, p -hydroxybenzoic acid, vanillic acid, syringic acid, p -coumaric acid, and ferulic acid. The presence of o - and m -hydroxybenzoic acids were suggested by mass fragmentography. The sources of those compounds are considered.

Comparative study on organic constituents in polluted and unpolluted inland aquatic environments—II: Features of fatty acids for polluted and unpolluted waters

Abstract Fatty acids were analyzed for polluted river waters from the Tokyo area and unpolluted river, brook, reservoir and pond waters from the Ogasawara (Bonin) Islands to elucidate their features for polluted and unpolluted waters. Fatty acids ranging from the carbon chain length of C8-C34 including unsaturated and branched acids were found with the great predominance of even-carbon numbers and lower molecular weight ranges (C13–C19) in the water samples from the Tokyo area and Ogasawara Islands. It was thus confirmed that no marked changes in fatty acid composition between polluted and unpolluted waters are absent. However, the total contents of the acids (average, 270 ± 120 μ g 1−1 at 90% confidence limits) as well as the FAC (fatty acids as carbon)/TOC (total organic carbon, 2.6 ± 0.93% ) and FAC/EOC (extractable organic carbon with ethyl acetate, 16 ± 6.7% ) of river water samples from the Tokyo area were considerably higher than those of the waters from the Ogasawara Islands ( 58 ± 29 μ g 1−1, 0.79 ± 0.48% and 2.1 ± 0.51% , respectively). These higher values for the Tokyo area should be due to sewage. A filtering method showed that most of fatty acids ( >95% ) was present in particulate fractions. In addition, the content of free fatty acids was fairly lower than that of combined fatty acids. Further, unsaturated fatty acids were detected only in combined forms both in particulate and dissolved fractions. They are considered to be present as esters in polluted and unpolluted waters.

Occurrence of 2-hydroxy acids in microalgae

Abstract 2-Hydroxy acids were believed to be absent in algae until this study, in which the analysis of microalgae belonging to Chlorophyta ( Chlamydomonas reinhardtii and Chlorella pyrenoidosa ), Rhodophyta ( Cyanidium caldarium M-8 and Cyanidium caldarium RK-1) and Cyanophyta ( Anbaena variabilis , Anacystis nidulans , Oscillatoria species and Phormidium foveolarum ) is reported. 2-Hydroxy adds with carbon chain lengths of C 16 -C 26 , were found in all the algal samples studied, ranging in concentrations from 4.0 to 320μg/g dry alga. The dominant constituents are 2-hydroxyhexadecanoic, 2-hydroxynonadecanoic, 2-hydroxyhexacosanoic and a branched 2-hydroxy-C 19 acid. The distribution patterns of the acids differed significantly among the algal samples. Hence 2-hydroxy acids may be useful for the classification of algal species as well as being an important source of 2-hydroxy acids in the natural environment.

Occurrence of 3-hydroxy acids in microalgae and cyanobacteria and their geochemical significance

Abstract 3-Hydroxy acids were detected in pure cultured microalgae: Chlorophyta— Chlamydomonas reinhardtii and Chlorella pyrenoidosa and Rhodophyta— Cyanidium caldarium (two strains), and cyanobacteria (Cyanophyta)— Anacystis nidulans, Phormidium foveolarum, Anabaena variabilis and Oscillatoria sp. Normal and branched (iso and anteiso) 3-hydroxy acids in the ranges of C 8 -C 26 were found in all the samples studied at concentrations ranging from 0.036 to 2.3 and 0.000 to 0.12 mg g −1 of dry sample, respectively. The major constituents were generally even-carbon numbered normal acids with carbon chain lengths below C 20 . Microalgae and cyanobacteria may be the important sources of 3-hydroxy acids in natural environments.

Comparative study on organic constituents in polluted and unpolluted inland aquatic environments—III: Phenols and aromatic acids in polluted and unpolluted waters

Abstract Phenols and aromatic acids were analysed in polluted river waters in the Tokyo area and in water from an unpolluted river, brook, reservoir and in pond waters from the Ogasawara (Bonin) Islands. The phenolic acids ( p -hydroxybenzoic, vanillic, syringic, p -coumaric and ferulic acids) and o - and m -hydroxybenzoic acids were found in the waters of the Tokyo area and Ogasawara Islands at a concentration of generally less than 1 μg 1 −1 , but pentachlorophenol, bisphenol A, terephthalic and trimesic acids were not identified in the waters of the Ogasawara Islands. It was confirmed that the major sources of these phenolic acids are vascular plants and their detritus, while pentachlorophenol, bisphenol A and terephthalic acids are mainly attributed to human activities. It was also established that these phenolic acids are commonly distributed in polluted and unpolluted waters. The p -coumaric and ferulic acids as carbon (CFC)/total organic carbon and CFC/extractable organic carbon with ethyl acetate values suggested that the contribution of vascular plants and their detritus to the waters between the Tokyo area and Ogasawara Islands are near equal. According to the syringic acid/vanillic acid ratios, it is probable that the relative contribution of angiosperms to gimnosperms for the waters of the Tokyo area is smaller than those of the Ogasawara Islands.

Gas chromatographic-mass spectrometric identification of phenolic acids in recent sediments

Saponification extraction of sediment samples was performed for the analysis of phenolic acids. After separation of phenolic acids by silica gel column chromatography, p-hydroxybenzoic, vanillic, syringic, p-coumaric (cis and trans), ferulic (cis and trans) and protocatechuic acids were identified, and the presence of o- and m-hydroxybenzoic acids was indicated by gas chromatography-mass spectrometry in lake, river and sea sediments. The content of each phenolic acid was less than 110 μg per gram of dry sample. These phenolic acids are mainly derived from vascular plants and their detritus.

Comparative study on organic constituents in polluted and unpolluted inland aquatic environments-I features of hydrocarbons for polluted and unpolluted waters

Abstract The constituents of hydrocarbons between highly polluted river waters collected from the Tokyo area and unpolluted river, brook, reservoir and pond waters obtained from the Ogasawara (Bonin) Islands were compared to characterize their features for polluted and unpolluted waters. n-Alkanes between the carbon chain length of C12 and C36, squalane and unresolved complex mixture of hydrocarbons (UCMH) were found in most of the river waters of the Tokyo area at the contents ranging from 0.026 to 14 μg 1−1, from 0.004 to 1.7 μg 1−1 and from less than 5 to 290 μg 1−1, respectively, whereas in the waters of the Ogasawara Islands, only n-alkanes ranging from C13 to C37 were found with the great predominance of odd-carbon numbers at the contents varying from 0.042 to 4.0 μg 1−1. It was indicated that the presence of squalane, UCMH and even-carbon numbered n-alkanes as the major constituents are intimately correlated with artificial hydrocarbon sources (fossil fuels and their products and both combustion products, and industrial products), while the great predominance of odd-carbon numbered n-alkanes for the unpolluted areas are mainly due to algae and higher plants. Besides, the major portion of n-alkanes, squalane and UCMH are thought to be present in polluted and unpolluted waters associated with particulate materials.

Changes in organic constituents in river water during incubation

Abstract A water sample collected from Tama River in the Tokyo area was incubated 29 days in the dark conditions at 25 ± 3°C to determine the extent and rate of the degradation of organic constituents and changes in their composition. The majority (>95%) of n -alkanes, fatty acids and sterols were degraded, although total organic carbon (TOC) and extractable organic carbon with ethyl acetate (EOC) remained in considerable amounts (>23%). The degradation of organic constituents occurred apparently in two or three steps. The rate constants for the degradation of TOC, EOC, hydrocarbons, fatty acids and sterols for the first step were 0.090, 0.18, 0.082, 1.4 and 0.23 day −1 , respectively. The relative abundances of total fatty acids and sterols as carbon in TOC (EOC) decreased remarkably during incubation (0–11 days) from 7.18 to 0.28% and 0.46 to 0.07%, respectively (31.2-2.2% and 2.0-0.6%, respectively), whereas those of hydrocarbons were not significantly changed.

Comparative study on organic constituents in polluted and unpolluted inland aquatic environments—V: Organic carbons and hydrocarbons in sediments

Abstract Organic carbons and hydrocarbons were analysed for polluted sediments from Tama River and sludges from night soil and sewage treatment plants in the Tokyo area and unpolluted sediments from river and reservoirs from Chichi-jima Island in the Ogasawara (Bonin) Islands to characterize their features for polluted and unpolluted aquatic environments. In addition the relationships of the features of organic constituents between waters and sediments were given. The contents of n-alkanes (C14-C36). squalane and unresolved complex mixture of hydrocarbons (UCMH) for the sediments from Tama River ranged from 16 to 94, 0.86–15 and 250–1100 μ g−1 dry base, which are much higher than those of the sediments from Chichi-jima Island. The major constituents of hydrocarbons in the sediments and sludges from the Tokyo area were mainly odd-carbon numbered n-alkanes and squalane, whereas those of the island were only odd-carbon numbered n-alkanes. Hydrocarbons as carbon (total content × 0.851. as C20H42, HCC)/total organic carbon (TOC), HCC/extractable organic carbon with ethyl acetate (EOC), squalane as carbon (SqC)/TOC. SqC/EOC and UCMH/n-Alkane (C15-C33) values for the sediments from Tama River were much higher than those of the sediments from the island, while carbon preference index (CPIH) values for the sediments of Tama River were considerably lower than those of the island. It was thus indicated that HCC/TOC, HCC/EOC, UCMH/n-Alkane and CPIH values should be the important indicators of hydrocarbon pollution for aquatic environments. In addition SqC/TOC and SqC/EOC ratios are apparently useful measures of urban-industrial activities on aquatic environments. The similarity of the nature of hydrocarbons of sediments and sludges from the Tokyo area indicated that the sewage contributed considerably to urban river sediments. Further it was also indicated that hydrocarbons were concentrated in sedimentary environments, although the features of hydrocarbons in sediments are generally similar to those of waters.

Comparative study on organic constituents in polluted and unpolluted inland aquatic environments-IV Indicators of hydrocarbon pollution for waters

Abstract The ratios between organic carbons and hydrocarbon constituents were compared for polluted river waters from the Tokyo area and unpolluted river, brook, reservoir and pond waters from the Ogasawara (Bonin) Islands to derive indicators of hydrocarbon pollution fossil fuels and their products and both combustion products, and industrial products. The hydrocarbons as carbon (HCC)/total organic carbon (TOC). HCC extractable organic carbon with ethyl acetate (EOC), squalane as carbon (SgC),TOC, SqC/EOC, and unresolved complex mixture of hydrocarbons (UCMH) n- Alkane (C 15 -C 33 ) ratios of the waters from the Tokyo area were much higher than those of the waters from the Ogasawara Islands. The values of carbon preference index (CPI 11 ) for n- alkanes (C 14 -C 14 ) close to unity were found in all the water samples from the Tokyo area. They are considerably lower than those of the water samples from the Ogasawara Islands. These results indicate that the HCC TOC, HCC/EOC UCMH/ n- Alkane and CPI 11 values are the important indicators of hydrocarbon pollution. Further, it was suggested that the SqC/TOC and SqC/EOC ratios are useful indicators of urban-industrial activities on water systems.