Analysis of organic substances in highly polluted river water by mass spectrometry

Yasuhara, Akio; Shiraishi, Hiroaki; Tsuji, Masahiko; Okuno, Toshihide

doi:10.1021/es00087a008

Cited by 41 publications

(12 citation statements)

References 13 publications

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“…The extraction efficiency already dramatically decreased for NP3EO to 15%. ,− Steam-distillable compounds can also be separated by vacuum distillation. In this case the evaporated water is trapped at −80 °C and then extracted with diethyl ether for 24 h with a continuous liquid−liquid extractor …”

Section: Liquid−liquid Extractionmentioning

confidence: 99%

“…Field desorption (FD) mass spectra of APEOs are dominated by quasimolecular ions [M + H] + , while structure-specific ions are often missing or of low intensity (Figure ). ,,− Therefore, the FD technique is less suited for structure elucidation but well suited to determine the molecular weight distribution of APEOs in technical surfactants and environmental samples. Levsen et al monitored the biodegradation of NPEOs by FD-MS enabling the temporal changes in the concentrations of the individual NPEO compounds. , Shiraishi et al used FD-MS to characterize fractions collected after HPLC separation of APEOs from river water. , They observed that the FD spectra were significantly affected by the presence of salts in the river water extracts, resulting in [M + alkali metal] + ions as the major ion species. , The combination of FD and the method of collisionally activated decomposition (CAD) in a tandem mass spectrometer gives spectra with a typical fragmentation pattern along with strong quasimolecular ions. In this way structure elucidation becomes possible with this technique …”

Section: Mass Spectrometrymentioning

confidence: 99%

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Alkylphenol Ethoxylates: Trace Analysis and Environmental Behavior

1997

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APEOs, the reader is referred to other books and reviews. [24][25][26][27][28][29] II. Analysis A. Sampling and StorageAnalytical results significantly depend on the homogeneity of the samples and accurate storage procedures which guarantee that no changes take place in the composition of the samples. The main problem of surfactants in general is their tendency to adsorb on all phase boundaries due to their amphiphilic nature. Consequently losses to surfaces or suspended solids from aqueous solutions are commonplace. Especially for matrices like sewage sludge, sediment, or soils, quantitative recovery of analytes turns out to be very difficult. Therefore, internal standards are added to the samples to correct for nonquantitative recovery during isolation and quantification of the analytes. Giger et al. used n-nonylbenzene 11,30 and 2,4,6-tribromophenol 8 in gas chromatographic determinations of APs/APEOs from sludge and water, respectively. 4-n-Nonylphenol, which is not included in technical NP, is applied to the quantification of NP in soils by GC. 31 For water analysis by HPLC 2,4,6-trimethylphenol is well suited. 32 This approach, however, is useless for nonspecific methods since they cannot discriminate analytes initially present from added internal standards.Environmental samples have to be preserved immediately upon collection with chemical biocides to minimize and prevent microbial degradation of the surfactant present. Water samples from sewage treatment plants, rivers, or seas are generally collected in glass bottles, preserved with 1% formaldehyde, and stored at 4 °C. [33][34][35][36][37] A less common preservation method for aqueous samples is the addition of methylene chloride and acidification to pH 2 with hydrochloric acid. 38 Kubeck et al. showed that refrigeration alone was sufficient to stabilize river water samples for up to 4 weeks. 35 Due to diurnal variations of APEO concentrations in the influents and effluents of sewage treatment plants, 24-h and 2-h composite samples should be collected, ideally, with automatic sampling devices. 39 Sewage sludges are dealt with in the same way as water samples, i.e. preservation with 1% formaldehyde and storage at 4 °C. 39,40 Jobst et al. preferred aluminium vessels to store the sludge samples. 41 Sediment samples are collected from the upper 2 cm using a grab sampler and frozen at -20 °C until analysis. 33,[42][43][44] In the laboratory, samples are freezedried 44 or air-dried at 21 °C43 .The application of sewage sludges to agricultural land has resulted in the need to monitor concentrations of detergents in sludge-amended soils. Soil samples are collected from the upper 5 cm with a stainless steel corer, dried at 60 °C, pulverized, and stored in the dark at 4 °C. 40 Biological matrices represent a difficult problem with regard to a representative sampling and a unchanged composition of the samples during storage. The Environmental Specimen Bank (ESB) of Germany has developed a method for collection and preparation of fresh biological materials. 45,46 ...

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Section: Liquid−liquid Extractionmentioning

confidence: 99%

Section: Mass Spectrometrymentioning

confidence: 99%

Alkylphenol Ethoxylates: Trace Analysis and Environmental Behavior

1997

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“…Contamination can be at extreme levels, as was the case involving the Hayashida River which was contaminated from leather manufacturing; detected concentrations of 2-BE were as high as 5.68 mg L -1 (Yasuhara et al 1981). The demonstrated presence of 2-BE in both untreated and treated waters illustrates that it is likely to present in waters that will undergo treatment, but also suggests that current treatment techniques are not be effective at removal.…”

Section: -Butoxyethanolmentioning

confidence: 99%

Photochemical fate of solvent constituents of Corexit oil dispersants

2014

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In 2010, an estimated 1.87 million gallons (7079 cubic meters) of chemical dispersants were applied to open ocean waters in the Gulf of Mexico as part of the response to the Deepwater Horizon blowout. This unprecedented volume of dispersant application highlighted the importance of dispersant chemical formulations, raising questions of dispersant fate and transport in the open ocean and spurring research into formulation improvements. The research presented here elucidates the contribution of photolytic processes to the degradation of two solvent constituents of these dispersant mixtures: propylene glycol (PG) and 2-butoxyethanol (2-BE). A series of photodegradation experiments were conducted to determine the contribution of direct photolysis and indirect photolysis via hydroxyl radical (HO) to compound degradation. Experiments were performed using both deep UV light sources (low pressure (LP) and medium pressure (MP) mercury vapor ultraviolet (UV) lamps) and a solar simulator. Sample matrices included ultrapure water, nitrate amended water, hydrogen peroxide (H2O2) spiked water, Gulf of Mexico seawater, and a surface water from Boulder, CO. Experiments included determination of the molar absorption coefficients (ε) and the HO reaction rate constants (kHO) of the individual compounds. Data illustrated that significant direct photolysis of either PG or 2-BE from sunlight is unlikely. The kHO for PG and 2-BE were determined to be 6.15 × 10(8) M(-1) s(-1) and 1.15 × 10(9) M(-1) s(-1), respectively. Solar simulation and UV experiments indicate that in natural systems, neither PG nor 2-BE is expected to undergo significant, rapid degradation due to direct or indirect photolysis. PG and 2-BE are effectively degraded through indirect photolysis in the presence of high HO concentrations, suggesting UV/H2O2 is a feasible possibility for the treatment of waters containing PG and 2-BE.

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“…In some earlier studies, field desorption mass spectrometry (FDMS) was used in the confirmation of OPE0 and NPEO in wastewater extracts (Otsuki and Shiraishi 1979;Yasuhara et al 1981;Crathome et al 1984). While major ions corresponding to the molecular masses of all APE0 oligomers were observed in one case (Otsuki and Shiraishi 1979), quasimolecular ions such as [M+Na]+, [M+K]+ and [M+H]+ were more commonly found in a FD mass spectrum (Yasuhara et al 1981;Crathome et al 1984). The latter phenomenon often occurred in surface water extracts where there were sufficient amounts of coextracted alkali salts to form these ions.…”

Section: Other Techniquesmentioning

confidence: 99%

Review of Analytical Methods for the Determination of Nonylphenol and Related Compounds in Environmental Samples

Lee

1999

Water Quality Research Journal

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Analytical methods published in the last 20 years for the extraction, chromato-graphic separation, and quantification of alkylphenol ethoxylates (APEO) and related compounds in environmental samples are reviewed. Examples of various isolation and preconcentration techniques for water, effluent, sediment and sludge are presented. This includes procedures from the classical liquid-liquid and Soxhlet extraction to the up-to-date solid phase and supercritical fluid extraction. Chromatographic separation of APEO by normal and reversed phase liquid chromatography (LC) and capillary column gas chromatography (GC) is compared. A variety of quantification methods involving the common LC and GC detectors as well as various mass spectrometric techniques are also discussed.

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Analysis of organic substances in highly polluted river water by mass spectrometry

Cited by 41 publications

References 13 publications

Alkylphenol Ethoxylates: Trace Analysis and Environmental Behavior

Alkylphenol Ethoxylates: Trace Analysis and Environmental Behavior

Photochemical fate of solvent constituents of Corexit oil dispersants

Review of Analytical Methods for the Determination of Nonylphenol and Related Compounds in Environmental Samples

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